Supporting Information Copper-Catalyzed SN2'-Selective Allylic ...
Supporting Information
Supporting Information
Copper-Catalyzed SN2’-Selective Allylic Substitution Reaction of gem-Diborylalkanes Zhen-Qi Zhang, Ben Zhang, Xi Lu, Jing-Hui Liu, Xiao-Yu Lu, Bin Xiao* and Yao Fu*
iChEM, CAS Key Laboratory of Urban Pollutant Conversion, Anhui Province Key Laboratory of Biomass Clean Energy, Department of Chemistry, University of Science and Technology of China, Hefei 230026, China.
Table of Contents I. General Information……………………………………………… ………………………………………………P2 ……………………………………………… II. Preparation of Substrates…………………………………… ……………………………………P3-P5 …………………………………… III. Copper-Catalyzed SN2’-Selective Allylic Substitution Reaction of gem-Diborylalkanes ……………………………………………P6-P21 …………………………………………… IV. References ………………………………………………………P22 ……………………………………………………… V. Spectral data………………………………………………… …………………………………………………P23-P71 …………………………………………………
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Supporting Information
I. General Information a. Materials All reactions were carried out in oven-dried Schlenk tubes under an argon or nitrogen atmosphere (purity ≥99.999%). The following chemicals were purchased and used as received: LiOtBu (J&K), LiOMe (J&K), KOtBu (Acros), NaOtBu (Acros), LiOEt (Aldrich), LiOiPr (Aldrich), Substituted Cinnamaldehydes and allylic alcohols were purchased from Adamas or J&K. Anhydrous DMF (Acros), anhydrous Toluene (Acros), anhydrous Dioxane (Acros), and anhydrous THF (Acros) were stored over 4 Å molecular sieves under an argon atmosphere in a septum-capped bottle. All other reagents and solvents mentioned in this text were purchased from commercial sources and used without purification. b. Analytical Methods 1
H,
11
B
13
C and
19
F-NMR spectra were recorded either on Bruker Avance 400 or
Varian Mercury 400 spectrometer at ambient temperature in CDCl3 unless otherwise noted;
11
B NMR signals are quoted relative to BF3⋅Et2O. Data for 1H-NMR are
reported as follows: chemical shift (δ ppm), multiplicity, integration, and coupling constant (Hz). Data for
13
C-NMR are reported in terms of chemical shift (δ ppm),
multiplicity, and coupling constant (Hz). Gas chromatographic (GC) analysis was acquired on a Shimadzu GC-2014 Series GC System equipped with a flame-ionization detector. GC-MS analysis was performed either on Thermo Scientific AS 3000 Series GC-MS System or Agilent 6890N gas chromatograph coupled to an Agilent 5973 inert mass selective detector. HRMS analysis was performed on Finnigan LCQ advantage Max Series MS System. Elementary Analysis was carried out on Elementar Vario EL III elemental analyzer.
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Supporting Information II. Preparation of Substrates
a. Preparation of allylic phosphates allylic phosphates were prepared according to literature procedure.[1] A 50 mL round-bottom flask charged with DMAP (N,N-dimethyl-4-aminopyridine, 0.12 g, 10 mol %) was evacuated and backfilled with argon. Anhydrous CH2Cl2 (10 mL), allylic alcohol (10 mmol) and pyridine (0.9 mL, 1.1 equiv) were added and the mixture was cooled with an ice bath. To the solution, diethylchlorophosphate (1.5 mL, 11 mmol, 1.1 equiv) was added dropwise and the mixture was stirred at 0 ºC for 5 min. The mixture was allowed to warm up to room temperature and stirred overnight at room temperature. The resulting mixture was diluted with ether (20 mL) and washed 1N HCl solution (15 mL × 3). The water layer was extracted with Et2O (20 mL × 3 ). The combined organic extracts were washed with saturated NaHCO3 aq. (15 mL × 3). The organic layer was dried over MgSO4. After filtration and removal of the solvents in vacuo, distillation gave allylic phosphates.
b. Preparation of 1,1-Diborylalkanes 1,1-Diborylalkanes were prepared according to literature procedure.[2] Method A. In air, Cu-catalyst (1 mmol), base (30 mmol), and diboron reagent (22 mmol) were added to a Schlenk tube equipped with a stir bar. The vessel was evacuated and filled with argon (three cycles). DMF (60 mL), and Dibromomethane (10 mmol) were added via syringe under an argon atmosphere. The reaction mixture was stirred at 40 oC for 24 h, and then diluted with EtOAc, filtered through silica gel with copious washings (Et2O or EtOAc), concentrated, and purified by column chromatography. Method B. In air, diborylmethane (10 mmol) was added to a Schlenk tube equipped with a stir bar. The vessel was evacuated and filled with argon (three cycles). THF (30 Page S3
Supporting Information mL), and LDA (11 mmol Acros) were added via syringe under an argon atmosphere at 0 oC. The reaction mixture was stirred for 5 min, and then alkyl halide (10 mmol) was added at the same tempurature. The reaction mixture was allowed to warm to room temperature and stirred for 2 hours. When reaction completed, reaction mixture diluted with Et2O, and quenched by the NH4Cl (aq), The organic layer was dried over Na2SO4 (s), filtered and concentrated in vacuo. and purified by column chromatography.
c. Preparation of the chiral N-heterocyclic carbene (NHC) ligands The chiral N-heterocyclic carbene (NHC) ligands were prepared according to literature procedure. [3] Step 1: Ethyl chloroglyoxylate (2.47 mL, 22.0 mmol) was added dropwise to a solution of 2,6- dimethylaniline (2.42 g, 20.0 mmol) and pyridine (1.77 mL, 22.0 mmol) in CH2Cl2 (20 mL) at 0 °C, and the resulting solution was stirred for 12 h at room temperature. The reaction mixture was diluted with EtOAc and washed successively with 1 M HCl aq, saturated NaHCO3aq, and saturated NaCl aq. The organic layer was dried over MgSO4, filtered, and concentrated under vacuum to afford ethyl 2,6-dimethylphenyloxamate as a pale pink solid. Step 2: A solution of ethyl 2,6-dimethylphenyloxamate (664 mg, 3.00 mmol) and amino alcohols (3.31 mmol) in CH2Cl2 (8.0 mL) was refluxed for 3 days. The reaction mixture was diluted with EtOAc and washed successively with 1 M HCl aq and saturated NaCl aq. The organic layer was dried over MgSO4, filtered, and concentrated under vacuum to afford the product as a white solid. This solid was added to a suspension of LiAlH4 (456 mg, 12.0 mmol) in THF (8.0 mL) at 0 °C, and the mixture was stirred for 20 h at 70 °C. The reaction was cooled to 0 °C, and H2O (0.4 mL), 15% NaOH aq (0.4 mL), and H2O (1.2 mL) were slowly added to it. The precipitate that formed was removed by filtration through celite with THF. The filtrate was concentrated under vacuum to afford substituted ethylenediamine as a pale Page S4
Supporting Information yellow oil. Step 3: HCl (3.0 mL, 3.0 mmol; 1.0 M solution in Et2O) was added dropwise to a solution of the substituted ethylenediamine which was obtained by step2 in Et2O (10 mL) and the mixture was stirred for 5 min at room temperature. This was then diluted with hexane and the resulting precipitate was collected by filtration. The solid thus obtained was dissolved in toluene (6.0 mL), and trimethyl orthoformate (1.42 mL, 13.0 mmol) was added to it. This mixture was stirred for 20 h at 90 °C, and the solvent was removed under vacuum. The residue was then dissolved in H2O (20 mL) and washed with EtOAc. KPF6 (1.11 g, 6.03 mmol) was added to the aqueous solution and the mixture was stirred for 12 h at room temperature. After extraction with CH2Cl2, the organic layer was dried over MgSO4, filtered, and concentrated under vacuum. The resulting solid was redissolved in CH2Cl2 and diluted with hexane. The precipitate that formed was collected by filtration to afford the chiral NHC ligand as a white solid.
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Supporting Information III. Copper-Catalyzed SN2’-Selective Allylic Substitution
Reaction of gem-Diborylalkanes Experimental Procedures for Examples Described in Scheme 2. In air, Cu-catalyst, base, ligand, were added to a Schlenk tube equipped with a stir bar. The vessel was evacuated and filled with argon (three cycles). Solvent (1.5 mL) was added in turn by syringe under argon atmosphere at room temperature, and then stirred at 60 oC for 30 min. Then diborylmethane was added in turn under an argon atmosphere and stirred at 60 oC for 10 min. And cinnamyl electrophiles (X = Cl, OPO(OEt)2, OAc or OCOOMe, 0.15 mmol) were added in turn under an argon atmosphere. The reaction mixture was stirred at 60 oC for 24 h, then diluted with EtOAc, filtered through silica gel with copious washings (Et2O or EtOAc), and Triphenylmethane (36.6 mg, 0.15 mmol) was added as internal standard. The product yield was determined by GC. Scheme 2. Optimization of the reaction conditions a
Entry 1b 2 3 4 5 6 7 8 9b 10 11
X OPO(OEt)2 OPO(OEt)2 OPO(OEt)2 OPO(OEt)2 OPO(OEt)2 OPO(OEt)2 OPO(OEt)2 OPO(OEt)2 OPO(OEt)2 Cl OAc
solvent DMF DMF THF dioxane dioxane dioxane dioxane dioxane dioxane dioxane dioxane
Ligand Yield (%) 88 87 66 68 SIMesHCl 72 IMesHCl 67 IPrHCl 23 L1 89 L1 64 L1 79 L1 trace
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1a:2a 8:92 4:96 83:17 87:13 85:15 80:20 82:18 97:3 96:4 90:10 -
Supporting Information 12 13 14 c 15 16 a
OCOOMe OPO(OEt)2 OPO(OEt)2 OPO(OEt)2 OPO(OEt)2
dioxane dioxane dioxane THF dioxane
L1 L1 SIMesHCl BINAP
22 75 84 trace
75:25 66:34 70:30 -
All reactions were carried out under 0.15 mmol scale, and 10 mol % CuCl, 3 equiv base , 2
equiv diborylmethane (1) and 1.5 mL solvent were used. The yields and the ratios of 1a:2a were determined by GC (average of two GC runs). b t-BuOLi was used instead of LiOMe. c CuI was used instead of CuCl.
Experimental Procedures for Examples Described in Scheme 3. General Procedure A. In air, CuCl 10 mol%, LiOMe 3 equiv., L1 13 mol%, were added to a Schlenk tube equipped with a stir bar. The vessel was evacuated and filled with argon (three cycles). Dioxane (2.0 mL) was added in turn by syringe under argon atmosphere at room temperature, and then stirred at 60 oC for 15 min. Then diborylmethane (1) was added in turn under an argon atmosphere and stirred at 60 oC for 10 min. And allylic phosphates (0.2 mmol) were added in turn under an argon atmosphere. The reaction mixture was stirred at 60 oC for 24 h. The reaction mixture was then diluted with EtOAc, filtered through silica gel with copious washings (Et2O or EtOAc), concentrated, and purified by column chromatography.
2-(2-(2-bromophenyl)but-3-en-1-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (2c)
Following general procedure A, 2b was used, (52mg, 77%). The product was isolated by flash chromatography (3% ethyl acetate/hexane) as pale yellow oil. 1H NMR (400 MHz, CDCl3) δ 7.52 (d, J = 7.8 Hz, 1H), 7.27 – 7.23 (m, 2H), 7.06 – 6.98 (m, 1H), 5.97 (ddd, J = 16.9, 10.4, 6.3 Hz, 1H), 5.04 (dt, J = 8.2, 1.4 Hz, 1H), 5.01 – 4.99 (m, 1H), 4.17 – 4.09 (m, 1H), 1.28 (d, J = 8.0 Hz, 2H), 1.14 (s, 6H), 1.12 (s, 6H).13C NMR (101 MHz, CDCl3) δ 144.57, 142.17, 132.92, 128.66, 127.63, 127.62, 124.76, 113.74, 83.30, 43.40, 24.81, 24.79. 11B NMR (128 MHz, CDCl3) δ 33.92.
HRMS (APCI) calcd for C16H23O2BBr + [(M+H)+]:337.0969; found: 337.0978.
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Supporting Information
2-(2-(4-bromophenyl)but-3-en-1-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (3c)
Following general procedure A, 3b was used, (56mg, 83%). The product was isolated by flash chromatography (3% ethyl acetate/hexane) as pale yellow oil. 1H NMR (400 MHz, CDCl3) δ 7.38 (d, J = 8.4 Hz, 2H), 7.10 (d, J = 8.3 Hz, 2H), 5.95 (ddd, J = 17.0, 10.2, 6.8 Hz, 1H), 5.07 – 4.91 (m, 2H), 3.57 (q, J = 7.5 Hz, 1H), 1.31 – 1.19 (m, 2H), 1.15 (s, 12H).13C NMR (101 MHz, CDCl3) δ 144.78, 143.23, 131.41, 129.43, 119.85, 113.40, 83.34, 44.51, 24.87, 24.85, 18.05.11B NMR (128 MHz, CDCl3) δ 33.97.
HRMS (APCI) calcd for C16H23O2BBr + [(M+H)+]:337.0969; found: 337.0978.
2-(2-(2-chlorophenyl)but-3-en-1-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (4c)
Following general procedure A, 4b was used, (46mg, 79%). The product was isolated by flash chromatography (3% ethyl acetate/hexane) as pale yellow oil. 1H NMR (400 MHz, CDCl3) δ 7.35 – 7.30 (m, 1H), 7.28 – 7.24 (m, 1H), 7.23 – 7.17 (m, 1H), 7.13 – 7.07 (m, 1H), 5.97 (ddd, J = 16.9, 10.3, 6.4 Hz, 1H), 5.07 – 4.96 (m, 2H), 4.20 – 4.12 (m, 1H), 1.33 – 1.22 (m, 2H), 1.14 (s, 6H), 1.12 (s, 6H).13C NMR (101 MHz, CDCl3) δ 142.89, 142.10, 133.84, 129.57, 128.48, 127.29, 126.96, 113.72, 83.29, 40.75, 24.81, 24.78. 11B NMR (128 MHz, CDCl3) δ 33.34.
HRMS (APCI) calcd for C16H23O2BCl + [(M+H)+]:293.1474; found: 293.1476.
2-(2-(3-chlorophenyl)but-3-en-1-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (5c)
Following general procedure A, 5b was used, (45mg, 77%). The product was isolated by flash chromatography (3% ethyl acetate/hexane) as pale yellow oil. 1H NMR (400 MHz, CDCl3) δ 7.25 – 7.06 (m, 4H), 5.97 (ddd, J = 17.1, 10.2, 6.8 Hz, 1H), 5.09 – 4.97 (m, 2H), 3.58 (q, J = 7.7 Hz, 1H), 1.33 – 1.19 (m, 2H), 1.15 (s, 12H).13C NMR (101 MHz, CDCl3) δ 147.88, 142.98, 134.09, 129.66, 127.94, 126.30, 125.81, 113.60, 83.36, 44.78, 24.87, 24.84.
11
B NMR (128 MHz,
CDCl3) δ 33.77.
HRMS (APCI) calcd for C16H23O2BCl + [(M+H)+]:293.1474; found: 293.1476.
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Supporting Information
2-(2-(4-chlorophenyl)but-3-en-1-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (6c)
Following general procedure A, 6b was used, (44mg, 76%). The product was isolated by flash chromatography (3% ethyl acetate/hexane) as pale yellow oil. 1H NMR (400 MHz, CDCl3) δ 7.25 – 7.21 (m, 2H), 7.18 – 7.13 (m, 2H), 5.95 (ddd, J = 17.0, 10.2, 6.8 Hz, 1H), 5.05 – 4.94 (m, 2H), 3.58 (q, J = 7.8 Hz, 1H), 1.31 – 1.20 (m, 2H), 1.14 (s, 12H).13C NMR (101 MHz, CDCl3) δ 144.24, 143.35, 131.78, 129.01, 128.46, 113.34, 83.34, 44.45, 24.87, 24.85.11B NMR (128 MHz, CDCl3) δ 33.50.
HRMS (APCI) calcd for C16H23O2BCl + [(M+H)+]:293.1474; found: 293.1476.
4,4,5,5-tetramethyl-2-(2-(4-nitrophenyl)but-3-en-1-yl)-1,3,2-dioxaborolane (7c)
Following general procedure A, 7b was used, (50mg, 82%). The product was isolated by flash chromatography (5% ethyl acetate/hexane) as yellow oil. 1H NMR (400 MHz, CDCl3) δ 8.15 – 8.08 (m, 2H), 7.40 – 7.33 (m, 2H), 5.95 (ddd, J = 17.1, 10.3, 6.8 Hz, 1H), 5.09 – 4.99 (m, 2H), 3.70 (q, J = 7.7 Hz, 1H), 1.36 – 1.19 (m, 2H), 1.13 (s, 6H), 1.12 (s, 6H).13C NMR (101 MHz, CDCl3) δ 153.58, 146.51, 142.09, 128.48, 123.66, 114.41, 83.47, 44.91, 24.81, 24.81, 18.08.11B NMR (128 MHz, CDCl3) δ 33.19.
HRMS (APCI) calcd for C16H23O4BN+ [(M+H)+]:304.1715; found: 304.1715.
2-(2-(4-fluorophenyl)but-3-en-1-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (8c)
Following general procedure A, 8b was used, (49mg, 88%). The product was isolated by flash chromatography (3% ethyl acetate/hexane) as pale yellow oil. 1H NMR (400 MHz, CDCl3) δ 7.22 – 7.13 (m, 2H), 6.99 – 6.89 (m, 2H), 5.97 (ddd, J = 17.0, 10.2, 6.7 Hz, 1H), 5.05 – 4.93 (m, 2H), 3.59 (q, J = 7.6 Hz, 1H), 1.32 – 1.17 (m, 2H), 1.13 (s, 12H).13C NMR (101 MHz, CDCl3) δ 161.44 (d, J = 243.5 Hz), 143.74, 141.36 (d, J = 3.1 Hz), 129.00 (d, J = 7.8 Hz), 115.02 (d, J = 21.1 Hz), 113.00, 83.26, 44.31, 24.83, 24.81, 18.39.
11
B NMR (128 MHz, CDCl3) δ 33.40. 19F NMR (376
MHz, CDCl3) δ -117.59.
HRMS (APCI) calcd for C16H23O2BF+ [(M+H)+]:277.1770; found: 277.1771.
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Supporting Information
4,4,5,5-tetramethyl-2-(2-(3-(trifluoromethyl)phenyl)but-3-en-1-yl)-1,3,2-dioxaborolane (9c)
Following general procedure A, 9b was used, (55mg, 85%). The product was isolated by flash chromatography (3% ethyl acetate/hexane) as pale yellow oil. 1H NMR (400 MHz, CDCl3) δ 7.56 – 7.30 (m, 4H), 5.99 (ddd, J = 17.0, 10.2, 6.7 Hz, 1H), 5.13 – 4.99 (m, 2H), 3.67 (q, J = 7.8 Hz, 1H), 1.35 – 1.20 (m, 2H), 1.13 (s, 12H).13C NMR (101 MHz, CDCl3) δ 146.68, 142.91, 131.09, 130.58 (q, J = 31.8 Hz), 128.80, 124.61 (q, J = 3.8 Hz), 124.43 (q, J = 272.3 Hz), 123.06 (q, J = 3.8 Hz), 113.79, 83.38, 44.87, 24.83, 24.78, 18.23.11B NMR (128 MHz, CDCl3) δ 33.74.19F NMR (376 MHz, CDCl3) δ -62.52.
HRMS (APCI) calcd for C17H23O2BF3+ [(M+H)+]:327.1738; found: 327.1740.
4-(1-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)but-3-en-2-yl)benzonitrile (10c)
Following general procedure A, 10b was used, (37mg, 77%). The product was isolated by flash chromatography (7% ethyl acetate/hexane) as pale yellow oil. 1H NMR (400 MHz, CDCl3) δ 7.56 (d, J = 8.3 Hz, 2H), 7.33 (d, J = 8.3 Hz, 2H), 5.94 (ddd, J = 17.1, 10.3, 6.8 Hz, 1H), 5.09 – 4.99 (m, 2H), 3.65 (q, J = 7.7 Hz, 1H), 1.34 – 1.27 (m, 1H), 1.24 – 1.18 (m, 1H), 1.14 (s, 6H), 1.13 (s, 6H).13C NMR (101 MHz, CDCl3) δ 151.41, 142.29, 132.29, 128.52, 119.28, 114.26, 109.99, 83.48, 45.15, 24.85, 24.83.11B NMR (128 MHz, CDCl3) δ 33.28.
HRMS (APCI) calcd for C17H23O2BN+ [(M+H)+]:284.1816; found: 284.1818.
4,4,5,5-tetramethyl-2-(2-vinylpentyl)-1,3,2-dioxaborolane (11c)
Following general procedure A, 11b or 12b was used, (26mg, 58%, or 23mg 52%). The product was isolated by flash chromatography (3% ethyl acetate/hexane) as pale yellow oil. 1H NMR (400 MHz, CDCl3) δ 5.66 (ddd, J = 17.2, 10.2, 8.3 Hz, 1H), 5.01 – 4.82 (m, 2H), 2.34 – 2.18 (m, 1H), 1.37 – 1.24 (m, 4H), 1.23 (s, 6H), 1.23 (s, 6H), 0.91 – 0.76 (m, 5H).13C NMR (101 MHz, CDCl3) δ 144.80, 112.79, 83.08, 39.72, 39.55, 25.03, 24.95, 20.48, 14.29.11B NMR (128 MHz, CDCl3) δ 33.60.
HRMS (APCI) calcd for C13H26O2B+ [(M+H)+]:225.2020; found: 225.2017.
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Supporting Information
(Z)-4,4,5,5-tetramethyl-2-(2-vinyloct-5-en-1-yl)-1,3,2-dioxaborolane (13c)
Following general procedure A, 13b was used, (30mg, 57%). The product was isolated by flash chromatography (3% ethyl acetate/hexane) as pale yellow oil. 1H NMR (400 MHz, CDCl3) δ 5.66 (ddd, J = 17.2, 10.2, 8.3 Hz, 1H), 5.37 – 5.24 (m, 2H), 5.02 – 4.85 (m, 2H), 2.34 – 2.21 (m, 1H), 2.07 – 1.93 (m, 4H), 1.45 – 1.27 (m, 2H), 1.22 (s, 12H), 0.93 (t, J = 7.5 Hz, 3H), 0.91 – 0.77 (m, 2H).13C NMR (101 MHz, CDCl3) δ 144.42, 131.68, 129.28, 113.21, 83.10, 39.54, 37.46, 25.10, 25.02, 24.95, 20.65, 17.78, 14.53.11B NMR (128 MHz, CDCl3) δ 33.67.
HRMS (APCI) calcd for C16H30O2B + [(M+H)+]:265.2333; found: 265.2336.
2-((4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)methyl)but-3-en-1-yl benzoate (14c)
Following general procedure A, 14b was used, (28mg, 45%). The product was isolated by flash chromatography (7% ethyl acetate/hexane) as pale yellow oil. 1H NMR (400 MHz, CDCl3) δ 8.07 – 8.00 (m, 2H), 7.57 – 7.51 (m, 1H), 7.46 – 7.39 (m, 2H), 5.90 – 5.77 (m, 1H), 5.19 – 5.00 (m, 2H), 4.25 (d, J = 6.5 Hz, 2H), 2.88 – 2.72 (m, 1H), 1.24 (s, 6H), 1.23 (s, 6H), 1.09 – 0.92 (m, 2H).13C NMR (101 MHz, CDCl3) δ 166.67, 140.39, 132.94, 130.61, 129.73, 128.43, 115.39, 83.40, 69.06, 38.98, 25.05, 24.89, 13.77.11B NMR (128 MHz, CDCl3) δ 33.55.
HRMS (APCI) calcd for C18H26O4B+ [(M+H)+]:317.1919; found: 317.1923. O B
O
O
S O
2-((4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)methyl)but-3-en-1-yl thiophene-2-carboxylate (15c)
Following general procedure A, 15b was used, (48mg, 75%). The product was isolated by flash chromatography (7% ethyl acetate/hexane) as pale yellow oil. 1H NMR (400 MHz, CDCl3) δ 7.78 (dd, J = 3.7, 1.2 Hz, 1H), 7.53 (dd, J = 5.0, 1.2 Hz, 1H), 7.08 (dd, J = 5.0, 3.8 Hz, 1H), 5.87 – 5.74 (m, 1H), 5.18 – 5.00 (m, 2H), 4.22 (d, J = 6.6 Hz, 2H), 2.84 – 2.70 (m, 1H), 1.24 (s, 6H), 1.23 (s, 6H), 1.11 – 0.85 (m, 2H).13C NMR (101 MHz, CDCl3) δ 162.32, 140.19, 134.20, 133.40, 132.34, 127.79, 115.50, 83.40, 69.14, 38.96, 25.05, 24.88.11B NMR (128 MHz, CDCl3) δ 33.98.
HRMS (APCI) calcd for C16H24O4BS+ [(M+H)+]:323.1483; found: 323.1484.
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Supporting Information
2-((4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)methyl)but-3-en-1-yl (16c)
furan-2-carboxylate
Following general procedure A, 16b was used, (33mg, 54%). The product was isolated by flash chromatography (7% ethyl acetate/hexane) as pale yellow oil. 1H NMR (400 MHz, CDCl3) δ 7.56 (d, J = 0.8 Hz, 1H), 7.14 (d, J = 3.5 Hz, 1H), 6.49 (dd, J = 3.5, 1.7 Hz, 1H), 5.86 – 5.73 (m, 1H), 5.12 (d, J = 17.2 Hz, 1H), 5.04 (d, J = 10.3 Hz, 1H), 4.26 – 4.19 (m, 2H), 2.83 – 2.69 (m, 1H), 1.23 (s, 6H), 1.22 (s, 6H), 1.07 – 0.83 (m, 2H).13C NMR (101 MHz, CDCl3) δ 158.87, 146.36, 144.93, 140.09, 117.84, 115.54, 111.87, 83.40, 68.90, 38.92, 25.04, 24.87.11B NMR (128 MHz, CDCl3) δ 33.91.
HRMS (APCI) calcd for C16H24O5B+ [(M+H)+]:307.1711; found: 307.1715.
2-(2-((benzyloxy)methyl)but-3-en-1-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (17c)
Following general procedure A, 17b was used, (47mg, 77%). The product was isolated by flash chromatography (4% ethyl acetate/hexane) as pale yellow oil. 1H NMR (400 MHz, CDCl3) δ 7.37 – 7.29 (m, 4H), 7.29 – 7.22 (m, 1H), 5.85 – 5.72 (m, 1H), 5.12 – 4.95 (m, 2H), 4.52 (s, 2H), 3.35 (ddd, J = 28.8, 9.1, 6.8 Hz, 2H), 2.73 – 2.61 (m, 1H), 1.20 (s, 12H), 1.01 – 0.90 (m, 1H), 0.89 – 0.80 (m, 1H).13C NMR (101 MHz, CDCl3) δ 141.57, 138.84, 128.42, 127.71, 127.52, 114.39, 83.15, 75.19, 72.91, 39.70, 24.98, 24.92.11B NMR (128 MHz, CDCl3) δ 34.51.
HRMS (APCI) calcd for C18H28O3B+ [(M+H)+]:303.2126; found: 303.2129.
tert-butyldimethyl((2-((4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)methyl)but-3-en-1-yl)oxy )silane (18c)
Following general procedure A, 18b was used, (40mg, 62%). The product was isolated by flash chromatography (3% ethyl acetate/hexane) as pale yellow oil. 1H NMR (400 MHz, CDCl3) δ 5.85 – 5.69 (m, 1H), 5.11 – 4.92 (m, 2H), 3.48 (d, J = 6.4 Hz, 2H), 2.52 – 2.34 (m, 1H), 1.23 (s, 6H), 1.22 (s, 6H), 1.01 – 0.91 (m, 1H), 0.88 (s, 9H), 0.83 – 0.73 (m, 1H), 0.03 (s, 6H).13C NMR (101 MHz, CDCl3) δ 141.70, 114.26, 83.11, 68.22, 42.13, 26.11, 25.05, 24.92, 18.52, -5.14, -5.15.11B NMR (128 MHz, CDCl3) δ 33.82.
HRMS (APCI) calcd for C17 H36O3SiB+ [(M+H)+]:327.2521; found: 327.2527.
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Supporting Information
(E)-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pent-2-en-1-yl benzoate (19c)
Following general procedure A, 19b was used, (43mg, 68%). The product was isolated by flash chromatography (3% ethyl acetate/hexane) as pale yellow oil. 1H NMR (400 MHz, CDCl3) δ 8.08 – 8.01 (m, 2H), 7.57 – 7.51 (m, 1H), 7.46 – 7.39 (m, 2H), 5.96 – 5.87 (m, 1H), 5.73 – 5.62 (m, 1H), 4.75 (dd, J = 6.4, 0.9 Hz, 2H), 2.21 (q, J = 6.8 Hz, 2H), 1.22 (s, 12H), 0.91 (t, J = 7.7 Hz, 2H).13C NMR (101 MHz, CDCl3) δ 166.56, 138.23, 132.95, 130.55, 129.73, 128.41, 123.00, 83.22, 65.89, 26.73, 24.94.11B NMR (128 MHz, CDCl3) δ 33.94.
HRMS (APCI) calcd for C18 H26O4B+ [(M+H)+]:317.1919; found: 317.1924.
2-(2,2-dimethylbut-3-en-1-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (20c)
Following general procedure A, but L2 was used as ligand, and 20b was used, (30mg, 72%). The product was isolated by flash chromatography (3% ethyl acetate/hexane) as pale yellow oil. 1H NMR (400 MHz, CDCl3) δ 5.92 (dd, J = 17.4, 10.6 Hz, 1H), 4.91 (dd, J = 17.4, 1.4 Hz, 1H), 4.82 (dd, J = 10.6, 1.4 Hz, 1H), 1.23 (s, 12H), 1.09 (s, 6H), 0.89 (s, 2H).13C NMR (101 MHz, CDCl3) δ 150.35, 108.86, 82.98, 35.43, 29.31, 25.03, 24.96.11B NMR (128 MHz, CDCl3) δ 33.20.
HRMS (APCI) calcd for C12 H24O2B+ [(M+H)+]:211.1864; found: 211.1866.
Optimization of conditions for the reaction of substituted gem-diborylalkanesa In air, Cu-catalyst, base, ligand, were added to a Schlenk tube equipped with a stir bar. The vessel was evacuated and filled with argon (three cycles). Solvent (1.5 mL) was added in turn by syringe under argon atmosphere at room temperature, and then stirred at 60 oC for 30 min. Then gem-diborylalkane (2, 2 equiv.) was added in turn under an argon atmosphere and stirred at 60 oC for 10 min. And cinnamyl electrophiles (X = OPO(OEt)2, 0.15 mmol) were added in turn under an argon atmosphere. The reaction mixture was stirred at 60 oC for 24 h, then diluted with EtOAc, filtered through silica gel with copious washings (Et2O or EtOAc), and
Page S13
Supporting Information Triphenylmethane (36.6 mg, 0.15 mmol) was added as internal standard. The product yield was determined by GC.
Entry Cat. X C1 OPO(OEt)2 1 C2 OPO(OEt)2 2 C3 OPO(OEt)2 3 C4 OPO(OEt)2 4 C5 OPO(OEt)2 5 C1 OPO(OEt)2 6 C2 OPO(OEt)2 7 C4 OPO(OEt)2 8 C5 OPO(OEt)2 9 10 CuCl OPO(OEt)2 11 CuCl OPO(OEt)2 12 CuCl OPO(OEt)2 13 CuI OPO(OEt)2 a
solvent dioxane dioxane dioxane dioxane dioxane THF THF THF THF dioxane THF dioxane DMF
Ligand Yield (%) 52 66 trace 62 77 67 56 79 80 L2 72 L2 63 5 4
Ratio of d.r. 1:2.2 1:2 1:2.6 1:2.8 1:3 1:2.3 1:3.8 1:3.2 1:2.7 1:2.3 -
All reactions were carried out under 0.15 mmol scale, and 10 mol % catalyst, 3 equiv
LiOMe , 2 equiv gem-diborylalkane (2) and 1.5 mL solvent were used. The yields and the ratios of 1d:1d’ and d.r. value were determined by GC (average of two GC runs). The ratios of 1d:1d’ of all the reactions were >91:9. Experimental Procedures for Examples Described in Scheme 4.
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Supporting Information General Procedure B. In air, C4 10 mol% and LiOMe 3 equiv. were added to a Schlenk tube equipped with a stir bar. The vessel was evacuated and filled with argon (three cycles). THF (2.0 mL) was added in turn by syringe under argon atmosphere at room temperature, and then stirred at 60 oC for 15 min. Then gem-diborylalkane (2, 2 equiv.) was added in turn under an argon atmosphere and stirred at 60 oC for 10 min. And allylic phosphates (0.2 mmol) were added in turn under an argon atmosphere. The reaction mixture was stirred at 60 oC for 24 h. The reaction mixture was then diluted with EtOAc, filtered through silica gel with copious washings (Et2O or EtOAc), concentrated, and purified by column chromatography.
4,4,5,5-tetramethyl-2-(3-phenylpent-4-en-2-yl)-1,3,2-dioxaborolane (1d)
Following general procedure B, 1b was used, (40mg, 74%). The product was isolated by flash chromatography (3% ethyl acetate/hexane) as pale yellow oil. 1H NMR (400 MHz, CDCl3) δ 7.45 – 7.08 (m, 5H), 6.15 – 5.98 (m, 0.22H), 5.97 – 5.78 (m, 0.77H), 5.23 – 4.90 (m, 2H), 3.38 – 3.17 (m, 1H), 1.57 – 1.41 (m, 1H), 1.28 (s, 1.2H), 1.27 (s, 1.2H), 1.06 (d, J = 7.3 Hz, 2.3H), 1.01 (s, 4.7H), 1.00 (s, 4.7H), 0.81 (d, J = 7.3 Hz, 0.6H). 13C NMR (101 MHz, CDCl3) δ 145.09, 142.09, 128.35, 127.96, 126.15, 114.70, 82.93, 53.44, 24.56, 24.49, 22.81, 13.91. 11B NMR (128 MHz, CDCl3) δ 33.56.
HRMS (APCI) calcd for C17 H26O2B+ [(M+H)+]:273.2020; found: 273.2025.
2-(3-(2-bromophenyl)pent-4-en-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (2d)
Following general procedure B, 2b was used, (36mg, 52%). The product was isolated by flash chromatography (3% ethyl acetate/hexane) as pale yellow oil. 1H NMR (400 MHz, CDCl3) δ 7.55 – 7.48 (m, 1H), 7.29 – 7.20 (m, 2H), 7.05 – 6.97 (m, 1H), 5.96 (ddd, J = 17.1, 10.2, 7.9 Hz, 0.30H), 5.73 (ddd, J = 17.0, 10.0, 8.6 Hz, 0.69H), 5.15 – 4.95 (m, 2H), 3.91 (dd, J = 10.9, 7.9 Hz, 0.29H), 3.79 (dd, J = 10.9, 8.7 Hz, 0.68H), 1.58 – 1.47 (m, 1H), 1.25 (s, 1.65H), 1.24 (s, 1.65H), 1.06 (d, J = 7.3 Hz, 2.05H), 0.98 (s, 4H), 0.95 (s, 4H), 0.82 (d, J = 7.3 Hz, 0.85H). 13C NMR (101 MHz, CDCl3) δ 143.92, 140.46, 132.91, 129.06, 127.55, 127.51, 124.96, 115.77, 83.03, 51.15, 24.50, 24.36, 13.81. 11B NMR (128 MHz, CDCl3) δ 33.63.
HRMS (APCI) calcd for C17 H25O2BBr+ [(M+H)+]:351.1126; found: 351.1126.
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Supporting Information
2-(3-(4-bromophenyl)pent-4-en-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (3d)
Following general procedure B, 3b was used, (45mg, 64%). The product was isolated by flash chromatography (3% ethyl acetate/hexane) as pale yellow oil. 1H NMR (400 MHz, CDCl3) δ 7.42 – 7.33 (m, 2H), 7.15 – 7.02 (m, 2H), 5.98 (ddd, J = 17.2, 10.2, 7.9 Hz, 0.16H), 5.87 – 5.72 (m, 0.84H), 5.09 – 4.93 (m, 2H), 3.28 – 3.15 (m, 1H), 1.41 (dq, J = 10.4, 7.3 Hz, 1H), 1.24 (s, 0.91H), 1.23 (s, 0.91H), 1.03 – 0.99 (m, 12H), 0.77 (d, J = 7.3 Hz, 0.44H). 13C NMR (101 MHz, CDCl3) δ 144.18, 141.44, 131.36, 129.78, 119.84, 115.22, 83.09, 52.71, 24.58, 24.56, 22.82, 13.82. 11B NMR (128 MHz, CDCl3) δ 33.51.
HRMS (APCI) calcd for C17 H25O2BBr+ [(M+H)+]:351.1126; found: 351.1125.
2-(3-(4-fluorophenyl)pent-4-en-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (4d)
Following general procedure B, 8b was used, (44mg, 75%). The product was isolated by flash chromatography (3% ethyl acetate/hexane) as pale yellow oil. 1H NMR (400 MHz, CDCl3) δ 7.22 – 7.10 (m, 2H), 7.00 – 6.90 (m, 2H), 5.99 (ddd, J = 17.1, 10.2, 7.9 Hz, 0.22H), 5.81 (ddd, J = 16.7, 10.3, 8.9 Hz, 0.79H), 5.08 – 4.95 (m, 2H), 3.27 (dd, J = 10.6, 8.0 Hz, 0.20H), 3.24 – 3.16 (m, 0.79H), 1.41 (dq, J = 10.7, 6.8 Hz, 1H), 1.24 (s, 1.13H), 1.23 (s, 1.13H), 1.02 (d, J = 7.3 Hz, 2.5H), 1.00 (s, 9.17H), 0.77 (d, J = 7.3 Hz, 0.58H). 13C NMR (101 MHz, CDCl3) δ 161.48 (d, J = 243.5 Hz),141.93, 140.90 (d, J = 3.1 Hz), 129.35 (d, J = 7.8 Hz), 114.90 (d, J = 7.2 Hz), 115.14, 83.03, 52.61, 24.57, 24.56, 13.94. 11B NMR (128 MHz, CDCl3) δ 33.38. 19F NMR (376 MHz, CDCl3) δ -117.48.
HRMS (APCI) calcd for C17 H25O2BF+ [(M+H)+]:291.1926; found: 291.1940.
Experimental Procedures for Examples Described in Scheme 5. General Procedure C. In air, C4 10 mol% and LiOMe 3 equiv. were added to a Schlenk tube equipped with a stir bar. The vessel was evacuated and filled with argon (three cycles). THF (2.0 mL) was added in turn by syringe under argon atmosphere at room temperature, and then stirred at 60 oC for 15 min. Then gem-diborylalkane (2 or Page S16
Supporting Information 3, 2 equiv.) was added in turn under an argon atmosphere and stirred at 60 oC for 10 min. And allylic epoxides (0.2 mmol) were added in turn under an argon atmosphere. The reaction mixture was stirred at 60 oC for 24 h. The reaction mixture was then diluted with EtOAc, filtered through silica gel with copious washings (Et2O or EtOAc), concentrated, and purified by column chromatography.
5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pent-2-en-1-ol (1e)
Following general procedure C, 1 was used, (28mg, 67%). The product was isolated by flash chromatography (30% ethyl acetate/hexane) as pale yellow oil. And product is a mixture of cis- and trans-((Z)- : (E)- = 1: 4). 1H NMR (400 MHz, CDCl3) δ 5.75 (dt, J = 15.2, 6.2 Hz, 1.2H), 5.62 (m, 1.2H), 4.16 (d, J = 7.1 Hz, 0.5H), 4.07 (dd, J = 5.9, 0.8 Hz, 2H), 2.30 – 2.09 (m, 2.5H), 1.24 (s, 15H), 0.97 – 0.83 (m, 2.5H).13C NMR (101 MHz, CDCl3) δ 135.32, 128.08, 83.23, 64.02, 26.65, 24.97.11B NMR (128 MHz, CDCl3) δ 33.94.
HRMS (APCI) calcd for C11 H22O3B+ [(M+H)+]:213.1657; found: 213.1657.
6-(naphthalen-1-yl)-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)hex-2-en-1-ol (2e)
Following general procedure C, 3 was used, (44mg, 62%). The product was isolated by flash chromatography (30% ethyl acetate/hexane) as pale yellow oil. And product is a mixture of cis- and trans-((Z)- : (E)- = 1: 5.6). 1H NMR (400 MHz, CDCl3) δ 8.05 (d, J = 8.2 Hz, 1H), 7.87 – 7.80 (m, 1H), 7.73 – 7.65 (m, 1H), 7.53 – 7.40 (m, 2H), 7.39 – 7.32 (m, 2H), 5.78 – 5.61 (m, 2.3H), 4.06 (d, J = 4.7 Hz, 2H), 3.23 (dd, J = 14.1, 8.6 Hz, 1H), 3.08 (dd, J = 14.1, 7.4 Hz, 1H), 2.92 (dd, J = 13.7, 8.6 Hz, 0.18H), 2.83 (dd, J = 13.8, 7.8 Hz, 0.18H), 2.33 – 2.17 (m, 2H), 1.70 – 1.55 (m, 1H), 1.17 (s, 6H), 1.12 (s, 6H).13C NMR (101 MHz, CDCl3) δ 137.95, 133.89, 132.51, 132.02, 129.98, 128.67, 126.59, 126.53, 125.64, 125.35, 125.23, 124.13, 83.23, 63.80, 34.07, 33.79, 24.85, 24.73.11B NMR (128 MHz, CDCl3) δ 34.52.
HRMS (APCI) calcd for C22 H29O3BNa+ [(M+Na)+]:375.2102; found: 375.2105.
Experimental of Scheme 6. Page S17
Supporting Information Asymmetric selectivity of the reaction of allylic phosphates with diborylmethane a
General Procedure D. In air, CuCl 10 mol%, LiOMe 3 equiv. and L2-4 13 mol% were added to a Schlenk tube equipped with a stir bar. The vessel was evacuated and filled with argon (three cycles). Dioxane (2.0 mL) was added in turn by syringe under argon atmosphere at room temperature, and then stirred at 60 oC for 15 min. Then diborylmethane (1) was added in turn under an argon atmosphere and stirred at 60 oC for 10 min. And allylic phosphates (0.2 mmol) were added in turn under an argon atmosphere. The reaction mixture was stirred at 60 oC for 24 h. The reaction mixture was then diluted with EtOAc, filtered through silica gel with copious washings (Et2O or EtOAc), concentrated, and purified by column chromatography. And then, the alkylboronic esters were dissolved in 1.0 mL THF, cooled to 0 °C and 2M aq. NaOH (0.25 mL) and 30% aq. H2O2 (0.25 mL) were added simultaneously. The mixture was warmed to RT and stirred for 1 hour. Sat. aq. NH4Cl (2 mL) and Et2O (2 mL) were added and the layers were separated. The aqueous phase was extracted with Et2O (2 × 3 mL) and the combined organics were washed with brine (5 mL), dried (MgSO4), concentrated in vacuo and purified by column chromatography.
2-phenylbut-3-en-1-ol (This compound was previously reported and our spectra data match
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Supporting Information those described, CAS: 6052-63-7 )[4]
Following general procedure D, light yellow oil. The ee was determined on a Daicel Chiralcel AD-H column with hexane/2-propanol = 95/5, flow = 0.5 mL/min. Retention times: 16.6 min [minor enantiomer], 17.4 min [major enantiomer]. 1
H NMR (400 MHz, CDCl3) δ 7.38 – 7.30 (m, 2H), 7.30 – 7.14 (m, 3H), 6.02 (ddd, J = 17.2, 10.4, 7.7
Hz, 1H), 5.32 – 5.08 (m, 2H), 3.82 (dd, J = 7.1, 1.1 Hz, 2H), 3.54 (q, J = 7.3 Hz, 1H), 1.76 (s, 1H). Racemate:
X= pinacol, L2
X= pinacol, L3
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Supporting Information
X= pinacol, L4
X= pinanediol, L3
X= pinanediol, L4
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Supporting Information
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Supporting Information IV. References [1] Semba, K.; Bessho, N.; Fujihara, T.; Terao, J.; Tsuji, Y. Angew. Chem. Int. Ed. 2014, 53, 9007. [2] Zhang, Z.-Q.; Yang, C.-T.; Liang, L.-J.; Xiao, B.; Lu, X.; Liu, J.-H.; Sun, Y.-Y.; Marder, T. B.; Fu, Y. Org. Lett. 2014, 16, 6342. [3] Shintani, R.; Takatsu, K.; Hayashi, T. Chem. Commun. 2010, 46, 6822. [4] Yu, B.; Menard, F.; Isono, N.; Lautens, M. Synthesis 2009, 2009, 853.
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Supporting Information Ⅴ. NMR Spectra and GC-MS Analysis 1
H NMR, 13C NMR and 11B NMR of 2-(2-(2-bromophenyl)but-3-en-1-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (2c)
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Supporting Information
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Supporting Information 1
H NMR, 13C NMR and 11B NMR of 2-(2-(4-bromophenyl)but-3-en-1-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (3c)
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Supporting Information
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Supporting Information 1
H NMR, 13C NMR and 11B NMR of 2-(2-(2-chlorophenyl)but-3-en-1-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (4c)
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Supporting Information
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Supporting Information 1
H NMR, 13C NMR and 11B NMR of 2-(2-(3-chlorophenyl)but-3-en-1-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (5c)
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Supporting Information
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Supporting Information 1
H NMR, 13C NMR and 11B NMR of 2-(2-(4-chlorophenyl)but-3-en-1-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (6c)
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Supporting Information
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Supporting Information 1
H NMR, 13C NMR and 11B NMR of
4,4,5,5-tetramethyl-2-(2-(4-nitrophenyl)but-3-en-1-yl)-1,3,2-dioxaborolane (7c)
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Supporting Information
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Supporting Information 1
H NMR, 13C NMR 11B NMR and 19F NMR of 2-(2-(4-fluorophenyl)but-3-en-1-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (8c)
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Supporting Information
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Supporting Information 1
H NMR, 13C NMR 11B NMR and 19F NMR of 4,4,5,5-tetramethyl-2-(2-(3-(trifluoromethyl)phenyl)but-3-en-1-yl)-1,3,2-dioxaborolane (9c)
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Supporting Information
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Supporting Information 1
H NMR, 13C NMR and 11B NMR of
4-(1-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)but-3-en-2-yl)benzonitrile (10c)
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Supporting Information
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Supporting Information 1
H NMR, 13C NMR and 11B NMR of
4,4,5,5-tetramethyl-2-(2-vinylpentyl)-1,3,2-dioxaborolane (11c)
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Supporting Information
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Supporting Information 1
H NMR, 13C NMR and 11B NMR of (Z)-4,4,5,5-tetramethyl-2-(2-vinyloct-5-en-1-yl)-1,3,2-dioxaborolane (13c)
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Supporting Information
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Supporting Information 1
H NMR, 13C NMR and 11B NMR of
2-((4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)methyl)but-3-en-1-yl benzoate (14c)
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Supporting Information
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Supporting Information 1
H NMR, 13C NMR and 11B NMR of 2-((4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)methyl)but-3-en-1-yl thiophene-2-carboxylate (15c)
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Supporting Information
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Supporting Information 1
H NMR, 13C NMR and 11B NMR of 2-((4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)methyl)but-3-en-1-yl furan-2-carboxylate (16c)
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Supporting Information
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Supporting Information 1
H NMR, 13C NMR and 11B NMR of 2-(2-((benzyloxy)methyl)but-3-en-1-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (17c)
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Supporting Information
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Supporting Information 1
H NMR, 13C NMR and 11B NMR of tert-butyldimethyl((2-((4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)methyl)but-3-en-1-yl)ox y)silane (18c)
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Supporting Information
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Supporting Information 1
H NMR, 13C NMR and 11B NMR of (E)-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pent-2-en-1-yl benzoate (19c)
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Supporting Information
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Supporting Information 1
H NMR, 13C NMR and 11B NMR of 2-(2,2-dimethylbut-3-en-1-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (20c)
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Supporting Information
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Supporting Information 1
H NMR, 13C NMR and 11B NMR of 4,4,5,5-tetramethyl-2-(3-phenylpent-4-en-2-yl)-1,3,2-dioxaborolane (1d)
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Supporting Information
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Supporting Information 1
H NMR, 13C NMR and 11B NMR of 2-(3-(2-bromophenyl)pent-4-en-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (2d)
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Supporting Information
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Supporting Information 1
H NMR, 13C NMR and 11B NMR of 2-(3-(4-bromophenyl)pent-4-en-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (3d)
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Supporting Information
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Supporting Information 1
H NMR, 13C NMR and 19F NMR of 2-(3-(4-fluorophenyl)pent-4-en-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (4d)
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Supporting Information
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Supporting Information 1
H NMR, 13C NMR and 11B NMR of 5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pent-2-en-1-ol (1e)
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Supporting Information
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Supporting Information 1
H NMR, 13C NMR and 11B NMR of 6-(naphthalen-1-yl)-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)hex-2-en-1-ol (2e)
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Supporting Information
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Supporting Information 1
H NMR, 13C NMR and 11B NMR of 2-phenylbut-3-en-1-ol
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Supporting Information
Copper-Catalyzed SN2’-Selective Allylic Substitution Reaction of gem-Diborylalkanes Zhen-Qi Zhang, Ben Zhang, Xi Lu, Jing-Hui Liu, Xiao-Yu Lu, Bin Xiao* and Yao Fu*
iChEM, CAS Key Laboratory of Urban Pollutant Conversion, Anhui Province Key Laboratory of Biomass Clean Energy, Department of Chemistry, University of Science and Technology of China, Hefei 230026, China.
Table of Contents I. General Information……………………………………………… ………………………………………………P2 ……………………………………………… II. Preparation of Substrates…………………………………… ……………………………………P3-P5 …………………………………… III. Copper-Catalyzed SN2’-Selective Allylic Substitution Reaction of gem-Diborylalkanes ……………………………………………P6-P21 …………………………………………… IV. References ………………………………………………………P22 ……………………………………………………… V. Spectral data………………………………………………… …………………………………………………P23-P71 …………………………………………………
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Supporting Information
I. General Information a. Materials All reactions were carried out in oven-dried Schlenk tubes under an argon or nitrogen atmosphere (purity ≥99.999%). The following chemicals were purchased and used as received: LiOtBu (J&K), LiOMe (J&K), KOtBu (Acros), NaOtBu (Acros), LiOEt (Aldrich), LiOiPr (Aldrich), Substituted Cinnamaldehydes and allylic alcohols were purchased from Adamas or J&K. Anhydrous DMF (Acros), anhydrous Toluene (Acros), anhydrous Dioxane (Acros), and anhydrous THF (Acros) were stored over 4 Å molecular sieves under an argon atmosphere in a septum-capped bottle. All other reagents and solvents mentioned in this text were purchased from commercial sources and used without purification. b. Analytical Methods 1
H,
11
B
13
C and
19
F-NMR spectra were recorded either on Bruker Avance 400 or
Varian Mercury 400 spectrometer at ambient temperature in CDCl3 unless otherwise noted;
11
B NMR signals are quoted relative to BF3⋅Et2O. Data for 1H-NMR are
reported as follows: chemical shift (δ ppm), multiplicity, integration, and coupling constant (Hz). Data for
13
C-NMR are reported in terms of chemical shift (δ ppm),
multiplicity, and coupling constant (Hz). Gas chromatographic (GC) analysis was acquired on a Shimadzu GC-2014 Series GC System equipped with a flame-ionization detector. GC-MS analysis was performed either on Thermo Scientific AS 3000 Series GC-MS System or Agilent 6890N gas chromatograph coupled to an Agilent 5973 inert mass selective detector. HRMS analysis was performed on Finnigan LCQ advantage Max Series MS System. Elementary Analysis was carried out on Elementar Vario EL III elemental analyzer.
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Supporting Information II. Preparation of Substrates
a. Preparation of allylic phosphates allylic phosphates were prepared according to literature procedure.[1] A 50 mL round-bottom flask charged with DMAP (N,N-dimethyl-4-aminopyridine, 0.12 g, 10 mol %) was evacuated and backfilled with argon. Anhydrous CH2Cl2 (10 mL), allylic alcohol (10 mmol) and pyridine (0.9 mL, 1.1 equiv) were added and the mixture was cooled with an ice bath. To the solution, diethylchlorophosphate (1.5 mL, 11 mmol, 1.1 equiv) was added dropwise and the mixture was stirred at 0 ºC for 5 min. The mixture was allowed to warm up to room temperature and stirred overnight at room temperature. The resulting mixture was diluted with ether (20 mL) and washed 1N HCl solution (15 mL × 3). The water layer was extracted with Et2O (20 mL × 3 ). The combined organic extracts were washed with saturated NaHCO3 aq. (15 mL × 3). The organic layer was dried over MgSO4. After filtration and removal of the solvents in vacuo, distillation gave allylic phosphates.
b. Preparation of 1,1-Diborylalkanes 1,1-Diborylalkanes were prepared according to literature procedure.[2] Method A. In air, Cu-catalyst (1 mmol), base (30 mmol), and diboron reagent (22 mmol) were added to a Schlenk tube equipped with a stir bar. The vessel was evacuated and filled with argon (three cycles). DMF (60 mL), and Dibromomethane (10 mmol) were added via syringe under an argon atmosphere. The reaction mixture was stirred at 40 oC for 24 h, and then diluted with EtOAc, filtered through silica gel with copious washings (Et2O or EtOAc), concentrated, and purified by column chromatography. Method B. In air, diborylmethane (10 mmol) was added to a Schlenk tube equipped with a stir bar. The vessel was evacuated and filled with argon (three cycles). THF (30 Page S3
Supporting Information mL), and LDA (11 mmol Acros) were added via syringe under an argon atmosphere at 0 oC. The reaction mixture was stirred for 5 min, and then alkyl halide (10 mmol) was added at the same tempurature. The reaction mixture was allowed to warm to room temperature and stirred for 2 hours. When reaction completed, reaction mixture diluted with Et2O, and quenched by the NH4Cl (aq), The organic layer was dried over Na2SO4 (s), filtered and concentrated in vacuo. and purified by column chromatography.
c. Preparation of the chiral N-heterocyclic carbene (NHC) ligands The chiral N-heterocyclic carbene (NHC) ligands were prepared according to literature procedure. [3] Step 1: Ethyl chloroglyoxylate (2.47 mL, 22.0 mmol) was added dropwise to a solution of 2,6- dimethylaniline (2.42 g, 20.0 mmol) and pyridine (1.77 mL, 22.0 mmol) in CH2Cl2 (20 mL) at 0 °C, and the resulting solution was stirred for 12 h at room temperature. The reaction mixture was diluted with EtOAc and washed successively with 1 M HCl aq, saturated NaHCO3aq, and saturated NaCl aq. The organic layer was dried over MgSO4, filtered, and concentrated under vacuum to afford ethyl 2,6-dimethylphenyloxamate as a pale pink solid. Step 2: A solution of ethyl 2,6-dimethylphenyloxamate (664 mg, 3.00 mmol) and amino alcohols (3.31 mmol) in CH2Cl2 (8.0 mL) was refluxed for 3 days. The reaction mixture was diluted with EtOAc and washed successively with 1 M HCl aq and saturated NaCl aq. The organic layer was dried over MgSO4, filtered, and concentrated under vacuum to afford the product as a white solid. This solid was added to a suspension of LiAlH4 (456 mg, 12.0 mmol) in THF (8.0 mL) at 0 °C, and the mixture was stirred for 20 h at 70 °C. The reaction was cooled to 0 °C, and H2O (0.4 mL), 15% NaOH aq (0.4 mL), and H2O (1.2 mL) were slowly added to it. The precipitate that formed was removed by filtration through celite with THF. The filtrate was concentrated under vacuum to afford substituted ethylenediamine as a pale Page S4
Supporting Information yellow oil. Step 3: HCl (3.0 mL, 3.0 mmol; 1.0 M solution in Et2O) was added dropwise to a solution of the substituted ethylenediamine which was obtained by step2 in Et2O (10 mL) and the mixture was stirred for 5 min at room temperature. This was then diluted with hexane and the resulting precipitate was collected by filtration. The solid thus obtained was dissolved in toluene (6.0 mL), and trimethyl orthoformate (1.42 mL, 13.0 mmol) was added to it. This mixture was stirred for 20 h at 90 °C, and the solvent was removed under vacuum. The residue was then dissolved in H2O (20 mL) and washed with EtOAc. KPF6 (1.11 g, 6.03 mmol) was added to the aqueous solution and the mixture was stirred for 12 h at room temperature. After extraction with CH2Cl2, the organic layer was dried over MgSO4, filtered, and concentrated under vacuum. The resulting solid was redissolved in CH2Cl2 and diluted with hexane. The precipitate that formed was collected by filtration to afford the chiral NHC ligand as a white solid.
Page S5
Supporting Information III. Copper-Catalyzed SN2’-Selective Allylic Substitution
Reaction of gem-Diborylalkanes Experimental Procedures for Examples Described in Scheme 2. In air, Cu-catalyst, base, ligand, were added to a Schlenk tube equipped with a stir bar. The vessel was evacuated and filled with argon (three cycles). Solvent (1.5 mL) was added in turn by syringe under argon atmosphere at room temperature, and then stirred at 60 oC for 30 min. Then diborylmethane was added in turn under an argon atmosphere and stirred at 60 oC for 10 min. And cinnamyl electrophiles (X = Cl, OPO(OEt)2, OAc or OCOOMe, 0.15 mmol) were added in turn under an argon atmosphere. The reaction mixture was stirred at 60 oC for 24 h, then diluted with EtOAc, filtered through silica gel with copious washings (Et2O or EtOAc), and Triphenylmethane (36.6 mg, 0.15 mmol) was added as internal standard. The product yield was determined by GC. Scheme 2. Optimization of the reaction conditions a
Entry 1b 2 3 4 5 6 7 8 9b 10 11
X OPO(OEt)2 OPO(OEt)2 OPO(OEt)2 OPO(OEt)2 OPO(OEt)2 OPO(OEt)2 OPO(OEt)2 OPO(OEt)2 OPO(OEt)2 Cl OAc
solvent DMF DMF THF dioxane dioxane dioxane dioxane dioxane dioxane dioxane dioxane
Ligand Yield (%) 88 87 66 68 SIMesHCl 72 IMesHCl 67 IPrHCl 23 L1 89 L1 64 L1 79 L1 trace
Page S6
1a:2a 8:92 4:96 83:17 87:13 85:15 80:20 82:18 97:3 96:4 90:10 -
Supporting Information 12 13 14 c 15 16 a
OCOOMe OPO(OEt)2 OPO(OEt)2 OPO(OEt)2 OPO(OEt)2
dioxane dioxane dioxane THF dioxane
L1 L1 SIMesHCl BINAP
22 75 84 trace
75:25 66:34 70:30 -
All reactions were carried out under 0.15 mmol scale, and 10 mol % CuCl, 3 equiv base , 2
equiv diborylmethane (1) and 1.5 mL solvent were used. The yields and the ratios of 1a:2a were determined by GC (average of two GC runs). b t-BuOLi was used instead of LiOMe. c CuI was used instead of CuCl.
Experimental Procedures for Examples Described in Scheme 3. General Procedure A. In air, CuCl 10 mol%, LiOMe 3 equiv., L1 13 mol%, were added to a Schlenk tube equipped with a stir bar. The vessel was evacuated and filled with argon (three cycles). Dioxane (2.0 mL) was added in turn by syringe under argon atmosphere at room temperature, and then stirred at 60 oC for 15 min. Then diborylmethane (1) was added in turn under an argon atmosphere and stirred at 60 oC for 10 min. And allylic phosphates (0.2 mmol) were added in turn under an argon atmosphere. The reaction mixture was stirred at 60 oC for 24 h. The reaction mixture was then diluted with EtOAc, filtered through silica gel with copious washings (Et2O or EtOAc), concentrated, and purified by column chromatography.
2-(2-(2-bromophenyl)but-3-en-1-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (2c)
Following general procedure A, 2b was used, (52mg, 77%). The product was isolated by flash chromatography (3% ethyl acetate/hexane) as pale yellow oil. 1H NMR (400 MHz, CDCl3) δ 7.52 (d, J = 7.8 Hz, 1H), 7.27 – 7.23 (m, 2H), 7.06 – 6.98 (m, 1H), 5.97 (ddd, J = 16.9, 10.4, 6.3 Hz, 1H), 5.04 (dt, J = 8.2, 1.4 Hz, 1H), 5.01 – 4.99 (m, 1H), 4.17 – 4.09 (m, 1H), 1.28 (d, J = 8.0 Hz, 2H), 1.14 (s, 6H), 1.12 (s, 6H).13C NMR (101 MHz, CDCl3) δ 144.57, 142.17, 132.92, 128.66, 127.63, 127.62, 124.76, 113.74, 83.30, 43.40, 24.81, 24.79. 11B NMR (128 MHz, CDCl3) δ 33.92.
HRMS (APCI) calcd for C16H23O2BBr + [(M+H)+]:337.0969; found: 337.0978.
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Supporting Information
2-(2-(4-bromophenyl)but-3-en-1-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (3c)
Following general procedure A, 3b was used, (56mg, 83%). The product was isolated by flash chromatography (3% ethyl acetate/hexane) as pale yellow oil. 1H NMR (400 MHz, CDCl3) δ 7.38 (d, J = 8.4 Hz, 2H), 7.10 (d, J = 8.3 Hz, 2H), 5.95 (ddd, J = 17.0, 10.2, 6.8 Hz, 1H), 5.07 – 4.91 (m, 2H), 3.57 (q, J = 7.5 Hz, 1H), 1.31 – 1.19 (m, 2H), 1.15 (s, 12H).13C NMR (101 MHz, CDCl3) δ 144.78, 143.23, 131.41, 129.43, 119.85, 113.40, 83.34, 44.51, 24.87, 24.85, 18.05.11B NMR (128 MHz, CDCl3) δ 33.97.
HRMS (APCI) calcd for C16H23O2BBr + [(M+H)+]:337.0969; found: 337.0978.
2-(2-(2-chlorophenyl)but-3-en-1-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (4c)
Following general procedure A, 4b was used, (46mg, 79%). The product was isolated by flash chromatography (3% ethyl acetate/hexane) as pale yellow oil. 1H NMR (400 MHz, CDCl3) δ 7.35 – 7.30 (m, 1H), 7.28 – 7.24 (m, 1H), 7.23 – 7.17 (m, 1H), 7.13 – 7.07 (m, 1H), 5.97 (ddd, J = 16.9, 10.3, 6.4 Hz, 1H), 5.07 – 4.96 (m, 2H), 4.20 – 4.12 (m, 1H), 1.33 – 1.22 (m, 2H), 1.14 (s, 6H), 1.12 (s, 6H).13C NMR (101 MHz, CDCl3) δ 142.89, 142.10, 133.84, 129.57, 128.48, 127.29, 126.96, 113.72, 83.29, 40.75, 24.81, 24.78. 11B NMR (128 MHz, CDCl3) δ 33.34.
HRMS (APCI) calcd for C16H23O2BCl + [(M+H)+]:293.1474; found: 293.1476.
2-(2-(3-chlorophenyl)but-3-en-1-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (5c)
Following general procedure A, 5b was used, (45mg, 77%). The product was isolated by flash chromatography (3% ethyl acetate/hexane) as pale yellow oil. 1H NMR (400 MHz, CDCl3) δ 7.25 – 7.06 (m, 4H), 5.97 (ddd, J = 17.1, 10.2, 6.8 Hz, 1H), 5.09 – 4.97 (m, 2H), 3.58 (q, J = 7.7 Hz, 1H), 1.33 – 1.19 (m, 2H), 1.15 (s, 12H).13C NMR (101 MHz, CDCl3) δ 147.88, 142.98, 134.09, 129.66, 127.94, 126.30, 125.81, 113.60, 83.36, 44.78, 24.87, 24.84.
11
B NMR (128 MHz,
CDCl3) δ 33.77.
HRMS (APCI) calcd for C16H23O2BCl + [(M+H)+]:293.1474; found: 293.1476.
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Supporting Information
2-(2-(4-chlorophenyl)but-3-en-1-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (6c)
Following general procedure A, 6b was used, (44mg, 76%). The product was isolated by flash chromatography (3% ethyl acetate/hexane) as pale yellow oil. 1H NMR (400 MHz, CDCl3) δ 7.25 – 7.21 (m, 2H), 7.18 – 7.13 (m, 2H), 5.95 (ddd, J = 17.0, 10.2, 6.8 Hz, 1H), 5.05 – 4.94 (m, 2H), 3.58 (q, J = 7.8 Hz, 1H), 1.31 – 1.20 (m, 2H), 1.14 (s, 12H).13C NMR (101 MHz, CDCl3) δ 144.24, 143.35, 131.78, 129.01, 128.46, 113.34, 83.34, 44.45, 24.87, 24.85.11B NMR (128 MHz, CDCl3) δ 33.50.
HRMS (APCI) calcd for C16H23O2BCl + [(M+H)+]:293.1474; found: 293.1476.
4,4,5,5-tetramethyl-2-(2-(4-nitrophenyl)but-3-en-1-yl)-1,3,2-dioxaborolane (7c)
Following general procedure A, 7b was used, (50mg, 82%). The product was isolated by flash chromatography (5% ethyl acetate/hexane) as yellow oil. 1H NMR (400 MHz, CDCl3) δ 8.15 – 8.08 (m, 2H), 7.40 – 7.33 (m, 2H), 5.95 (ddd, J = 17.1, 10.3, 6.8 Hz, 1H), 5.09 – 4.99 (m, 2H), 3.70 (q, J = 7.7 Hz, 1H), 1.36 – 1.19 (m, 2H), 1.13 (s, 6H), 1.12 (s, 6H).13C NMR (101 MHz, CDCl3) δ 153.58, 146.51, 142.09, 128.48, 123.66, 114.41, 83.47, 44.91, 24.81, 24.81, 18.08.11B NMR (128 MHz, CDCl3) δ 33.19.
HRMS (APCI) calcd for C16H23O4BN+ [(M+H)+]:304.1715; found: 304.1715.
2-(2-(4-fluorophenyl)but-3-en-1-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (8c)
Following general procedure A, 8b was used, (49mg, 88%). The product was isolated by flash chromatography (3% ethyl acetate/hexane) as pale yellow oil. 1H NMR (400 MHz, CDCl3) δ 7.22 – 7.13 (m, 2H), 6.99 – 6.89 (m, 2H), 5.97 (ddd, J = 17.0, 10.2, 6.7 Hz, 1H), 5.05 – 4.93 (m, 2H), 3.59 (q, J = 7.6 Hz, 1H), 1.32 – 1.17 (m, 2H), 1.13 (s, 12H).13C NMR (101 MHz, CDCl3) δ 161.44 (d, J = 243.5 Hz), 143.74, 141.36 (d, J = 3.1 Hz), 129.00 (d, J = 7.8 Hz), 115.02 (d, J = 21.1 Hz), 113.00, 83.26, 44.31, 24.83, 24.81, 18.39.
11
B NMR (128 MHz, CDCl3) δ 33.40. 19F NMR (376
MHz, CDCl3) δ -117.59.
HRMS (APCI) calcd for C16H23O2BF+ [(M+H)+]:277.1770; found: 277.1771.
Page S9
Supporting Information
4,4,5,5-tetramethyl-2-(2-(3-(trifluoromethyl)phenyl)but-3-en-1-yl)-1,3,2-dioxaborolane (9c)
Following general procedure A, 9b was used, (55mg, 85%). The product was isolated by flash chromatography (3% ethyl acetate/hexane) as pale yellow oil. 1H NMR (400 MHz, CDCl3) δ 7.56 – 7.30 (m, 4H), 5.99 (ddd, J = 17.0, 10.2, 6.7 Hz, 1H), 5.13 – 4.99 (m, 2H), 3.67 (q, J = 7.8 Hz, 1H), 1.35 – 1.20 (m, 2H), 1.13 (s, 12H).13C NMR (101 MHz, CDCl3) δ 146.68, 142.91, 131.09, 130.58 (q, J = 31.8 Hz), 128.80, 124.61 (q, J = 3.8 Hz), 124.43 (q, J = 272.3 Hz), 123.06 (q, J = 3.8 Hz), 113.79, 83.38, 44.87, 24.83, 24.78, 18.23.11B NMR (128 MHz, CDCl3) δ 33.74.19F NMR (376 MHz, CDCl3) δ -62.52.
HRMS (APCI) calcd for C17H23O2BF3+ [(M+H)+]:327.1738; found: 327.1740.
4-(1-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)but-3-en-2-yl)benzonitrile (10c)
Following general procedure A, 10b was used, (37mg, 77%). The product was isolated by flash chromatography (7% ethyl acetate/hexane) as pale yellow oil. 1H NMR (400 MHz, CDCl3) δ 7.56 (d, J = 8.3 Hz, 2H), 7.33 (d, J = 8.3 Hz, 2H), 5.94 (ddd, J = 17.1, 10.3, 6.8 Hz, 1H), 5.09 – 4.99 (m, 2H), 3.65 (q, J = 7.7 Hz, 1H), 1.34 – 1.27 (m, 1H), 1.24 – 1.18 (m, 1H), 1.14 (s, 6H), 1.13 (s, 6H).13C NMR (101 MHz, CDCl3) δ 151.41, 142.29, 132.29, 128.52, 119.28, 114.26, 109.99, 83.48, 45.15, 24.85, 24.83.11B NMR (128 MHz, CDCl3) δ 33.28.
HRMS (APCI) calcd for C17H23O2BN+ [(M+H)+]:284.1816; found: 284.1818.
4,4,5,5-tetramethyl-2-(2-vinylpentyl)-1,3,2-dioxaborolane (11c)
Following general procedure A, 11b or 12b was used, (26mg, 58%, or 23mg 52%). The product was isolated by flash chromatography (3% ethyl acetate/hexane) as pale yellow oil. 1H NMR (400 MHz, CDCl3) δ 5.66 (ddd, J = 17.2, 10.2, 8.3 Hz, 1H), 5.01 – 4.82 (m, 2H), 2.34 – 2.18 (m, 1H), 1.37 – 1.24 (m, 4H), 1.23 (s, 6H), 1.23 (s, 6H), 0.91 – 0.76 (m, 5H).13C NMR (101 MHz, CDCl3) δ 144.80, 112.79, 83.08, 39.72, 39.55, 25.03, 24.95, 20.48, 14.29.11B NMR (128 MHz, CDCl3) δ 33.60.
HRMS (APCI) calcd for C13H26O2B+ [(M+H)+]:225.2020; found: 225.2017.
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Supporting Information
(Z)-4,4,5,5-tetramethyl-2-(2-vinyloct-5-en-1-yl)-1,3,2-dioxaborolane (13c)
Following general procedure A, 13b was used, (30mg, 57%). The product was isolated by flash chromatography (3% ethyl acetate/hexane) as pale yellow oil. 1H NMR (400 MHz, CDCl3) δ 5.66 (ddd, J = 17.2, 10.2, 8.3 Hz, 1H), 5.37 – 5.24 (m, 2H), 5.02 – 4.85 (m, 2H), 2.34 – 2.21 (m, 1H), 2.07 – 1.93 (m, 4H), 1.45 – 1.27 (m, 2H), 1.22 (s, 12H), 0.93 (t, J = 7.5 Hz, 3H), 0.91 – 0.77 (m, 2H).13C NMR (101 MHz, CDCl3) δ 144.42, 131.68, 129.28, 113.21, 83.10, 39.54, 37.46, 25.10, 25.02, 24.95, 20.65, 17.78, 14.53.11B NMR (128 MHz, CDCl3) δ 33.67.
HRMS (APCI) calcd for C16H30O2B + [(M+H)+]:265.2333; found: 265.2336.
2-((4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)methyl)but-3-en-1-yl benzoate (14c)
Following general procedure A, 14b was used, (28mg, 45%). The product was isolated by flash chromatography (7% ethyl acetate/hexane) as pale yellow oil. 1H NMR (400 MHz, CDCl3) δ 8.07 – 8.00 (m, 2H), 7.57 – 7.51 (m, 1H), 7.46 – 7.39 (m, 2H), 5.90 – 5.77 (m, 1H), 5.19 – 5.00 (m, 2H), 4.25 (d, J = 6.5 Hz, 2H), 2.88 – 2.72 (m, 1H), 1.24 (s, 6H), 1.23 (s, 6H), 1.09 – 0.92 (m, 2H).13C NMR (101 MHz, CDCl3) δ 166.67, 140.39, 132.94, 130.61, 129.73, 128.43, 115.39, 83.40, 69.06, 38.98, 25.05, 24.89, 13.77.11B NMR (128 MHz, CDCl3) δ 33.55.
HRMS (APCI) calcd for C18H26O4B+ [(M+H)+]:317.1919; found: 317.1923. O B
O
O
S O
2-((4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)methyl)but-3-en-1-yl thiophene-2-carboxylate (15c)
Following general procedure A, 15b was used, (48mg, 75%). The product was isolated by flash chromatography (7% ethyl acetate/hexane) as pale yellow oil. 1H NMR (400 MHz, CDCl3) δ 7.78 (dd, J = 3.7, 1.2 Hz, 1H), 7.53 (dd, J = 5.0, 1.2 Hz, 1H), 7.08 (dd, J = 5.0, 3.8 Hz, 1H), 5.87 – 5.74 (m, 1H), 5.18 – 5.00 (m, 2H), 4.22 (d, J = 6.6 Hz, 2H), 2.84 – 2.70 (m, 1H), 1.24 (s, 6H), 1.23 (s, 6H), 1.11 – 0.85 (m, 2H).13C NMR (101 MHz, CDCl3) δ 162.32, 140.19, 134.20, 133.40, 132.34, 127.79, 115.50, 83.40, 69.14, 38.96, 25.05, 24.88.11B NMR (128 MHz, CDCl3) δ 33.98.
HRMS (APCI) calcd for C16H24O4BS+ [(M+H)+]:323.1483; found: 323.1484.
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Supporting Information
2-((4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)methyl)but-3-en-1-yl (16c)
furan-2-carboxylate
Following general procedure A, 16b was used, (33mg, 54%). The product was isolated by flash chromatography (7% ethyl acetate/hexane) as pale yellow oil. 1H NMR (400 MHz, CDCl3) δ 7.56 (d, J = 0.8 Hz, 1H), 7.14 (d, J = 3.5 Hz, 1H), 6.49 (dd, J = 3.5, 1.7 Hz, 1H), 5.86 – 5.73 (m, 1H), 5.12 (d, J = 17.2 Hz, 1H), 5.04 (d, J = 10.3 Hz, 1H), 4.26 – 4.19 (m, 2H), 2.83 – 2.69 (m, 1H), 1.23 (s, 6H), 1.22 (s, 6H), 1.07 – 0.83 (m, 2H).13C NMR (101 MHz, CDCl3) δ 158.87, 146.36, 144.93, 140.09, 117.84, 115.54, 111.87, 83.40, 68.90, 38.92, 25.04, 24.87.11B NMR (128 MHz, CDCl3) δ 33.91.
HRMS (APCI) calcd for C16H24O5B+ [(M+H)+]:307.1711; found: 307.1715.
2-(2-((benzyloxy)methyl)but-3-en-1-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (17c)
Following general procedure A, 17b was used, (47mg, 77%). The product was isolated by flash chromatography (4% ethyl acetate/hexane) as pale yellow oil. 1H NMR (400 MHz, CDCl3) δ 7.37 – 7.29 (m, 4H), 7.29 – 7.22 (m, 1H), 5.85 – 5.72 (m, 1H), 5.12 – 4.95 (m, 2H), 4.52 (s, 2H), 3.35 (ddd, J = 28.8, 9.1, 6.8 Hz, 2H), 2.73 – 2.61 (m, 1H), 1.20 (s, 12H), 1.01 – 0.90 (m, 1H), 0.89 – 0.80 (m, 1H).13C NMR (101 MHz, CDCl3) δ 141.57, 138.84, 128.42, 127.71, 127.52, 114.39, 83.15, 75.19, 72.91, 39.70, 24.98, 24.92.11B NMR (128 MHz, CDCl3) δ 34.51.
HRMS (APCI) calcd for C18H28O3B+ [(M+H)+]:303.2126; found: 303.2129.
tert-butyldimethyl((2-((4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)methyl)but-3-en-1-yl)oxy )silane (18c)
Following general procedure A, 18b was used, (40mg, 62%). The product was isolated by flash chromatography (3% ethyl acetate/hexane) as pale yellow oil. 1H NMR (400 MHz, CDCl3) δ 5.85 – 5.69 (m, 1H), 5.11 – 4.92 (m, 2H), 3.48 (d, J = 6.4 Hz, 2H), 2.52 – 2.34 (m, 1H), 1.23 (s, 6H), 1.22 (s, 6H), 1.01 – 0.91 (m, 1H), 0.88 (s, 9H), 0.83 – 0.73 (m, 1H), 0.03 (s, 6H).13C NMR (101 MHz, CDCl3) δ 141.70, 114.26, 83.11, 68.22, 42.13, 26.11, 25.05, 24.92, 18.52, -5.14, -5.15.11B NMR (128 MHz, CDCl3) δ 33.82.
HRMS (APCI) calcd for C17 H36O3SiB+ [(M+H)+]:327.2521; found: 327.2527.
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Supporting Information
(E)-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pent-2-en-1-yl benzoate (19c)
Following general procedure A, 19b was used, (43mg, 68%). The product was isolated by flash chromatography (3% ethyl acetate/hexane) as pale yellow oil. 1H NMR (400 MHz, CDCl3) δ 8.08 – 8.01 (m, 2H), 7.57 – 7.51 (m, 1H), 7.46 – 7.39 (m, 2H), 5.96 – 5.87 (m, 1H), 5.73 – 5.62 (m, 1H), 4.75 (dd, J = 6.4, 0.9 Hz, 2H), 2.21 (q, J = 6.8 Hz, 2H), 1.22 (s, 12H), 0.91 (t, J = 7.7 Hz, 2H).13C NMR (101 MHz, CDCl3) δ 166.56, 138.23, 132.95, 130.55, 129.73, 128.41, 123.00, 83.22, 65.89, 26.73, 24.94.11B NMR (128 MHz, CDCl3) δ 33.94.
HRMS (APCI) calcd for C18 H26O4B+ [(M+H)+]:317.1919; found: 317.1924.
2-(2,2-dimethylbut-3-en-1-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (20c)
Following general procedure A, but L2 was used as ligand, and 20b was used, (30mg, 72%). The product was isolated by flash chromatography (3% ethyl acetate/hexane) as pale yellow oil. 1H NMR (400 MHz, CDCl3) δ 5.92 (dd, J = 17.4, 10.6 Hz, 1H), 4.91 (dd, J = 17.4, 1.4 Hz, 1H), 4.82 (dd, J = 10.6, 1.4 Hz, 1H), 1.23 (s, 12H), 1.09 (s, 6H), 0.89 (s, 2H).13C NMR (101 MHz, CDCl3) δ 150.35, 108.86, 82.98, 35.43, 29.31, 25.03, 24.96.11B NMR (128 MHz, CDCl3) δ 33.20.
HRMS (APCI) calcd for C12 H24O2B+ [(M+H)+]:211.1864; found: 211.1866.
Optimization of conditions for the reaction of substituted gem-diborylalkanesa In air, Cu-catalyst, base, ligand, were added to a Schlenk tube equipped with a stir bar. The vessel was evacuated and filled with argon (three cycles). Solvent (1.5 mL) was added in turn by syringe under argon atmosphere at room temperature, and then stirred at 60 oC for 30 min. Then gem-diborylalkane (2, 2 equiv.) was added in turn under an argon atmosphere and stirred at 60 oC for 10 min. And cinnamyl electrophiles (X = OPO(OEt)2, 0.15 mmol) were added in turn under an argon atmosphere. The reaction mixture was stirred at 60 oC for 24 h, then diluted with EtOAc, filtered through silica gel with copious washings (Et2O or EtOAc), and
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Supporting Information Triphenylmethane (36.6 mg, 0.15 mmol) was added as internal standard. The product yield was determined by GC.
Entry Cat. X C1 OPO(OEt)2 1 C2 OPO(OEt)2 2 C3 OPO(OEt)2 3 C4 OPO(OEt)2 4 C5 OPO(OEt)2 5 C1 OPO(OEt)2 6 C2 OPO(OEt)2 7 C4 OPO(OEt)2 8 C5 OPO(OEt)2 9 10 CuCl OPO(OEt)2 11 CuCl OPO(OEt)2 12 CuCl OPO(OEt)2 13 CuI OPO(OEt)2 a
solvent dioxane dioxane dioxane dioxane dioxane THF THF THF THF dioxane THF dioxane DMF
Ligand Yield (%) 52 66 trace 62 77 67 56 79 80 L2 72 L2 63 5 4
Ratio of d.r. 1:2.2 1:2 1:2.6 1:2.8 1:3 1:2.3 1:3.8 1:3.2 1:2.7 1:2.3 -
All reactions were carried out under 0.15 mmol scale, and 10 mol % catalyst, 3 equiv
LiOMe , 2 equiv gem-diborylalkane (2) and 1.5 mL solvent were used. The yields and the ratios of 1d:1d’ and d.r. value were determined by GC (average of two GC runs). The ratios of 1d:1d’ of all the reactions were >91:9. Experimental Procedures for Examples Described in Scheme 4.
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Supporting Information General Procedure B. In air, C4 10 mol% and LiOMe 3 equiv. were added to a Schlenk tube equipped with a stir bar. The vessel was evacuated and filled with argon (three cycles). THF (2.0 mL) was added in turn by syringe under argon atmosphere at room temperature, and then stirred at 60 oC for 15 min. Then gem-diborylalkane (2, 2 equiv.) was added in turn under an argon atmosphere and stirred at 60 oC for 10 min. And allylic phosphates (0.2 mmol) were added in turn under an argon atmosphere. The reaction mixture was stirred at 60 oC for 24 h. The reaction mixture was then diluted with EtOAc, filtered through silica gel with copious washings (Et2O or EtOAc), concentrated, and purified by column chromatography.
4,4,5,5-tetramethyl-2-(3-phenylpent-4-en-2-yl)-1,3,2-dioxaborolane (1d)
Following general procedure B, 1b was used, (40mg, 74%). The product was isolated by flash chromatography (3% ethyl acetate/hexane) as pale yellow oil. 1H NMR (400 MHz, CDCl3) δ 7.45 – 7.08 (m, 5H), 6.15 – 5.98 (m, 0.22H), 5.97 – 5.78 (m, 0.77H), 5.23 – 4.90 (m, 2H), 3.38 – 3.17 (m, 1H), 1.57 – 1.41 (m, 1H), 1.28 (s, 1.2H), 1.27 (s, 1.2H), 1.06 (d, J = 7.3 Hz, 2.3H), 1.01 (s, 4.7H), 1.00 (s, 4.7H), 0.81 (d, J = 7.3 Hz, 0.6H). 13C NMR (101 MHz, CDCl3) δ 145.09, 142.09, 128.35, 127.96, 126.15, 114.70, 82.93, 53.44, 24.56, 24.49, 22.81, 13.91. 11B NMR (128 MHz, CDCl3) δ 33.56.
HRMS (APCI) calcd for C17 H26O2B+ [(M+H)+]:273.2020; found: 273.2025.
2-(3-(2-bromophenyl)pent-4-en-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (2d)
Following general procedure B, 2b was used, (36mg, 52%). The product was isolated by flash chromatography (3% ethyl acetate/hexane) as pale yellow oil. 1H NMR (400 MHz, CDCl3) δ 7.55 – 7.48 (m, 1H), 7.29 – 7.20 (m, 2H), 7.05 – 6.97 (m, 1H), 5.96 (ddd, J = 17.1, 10.2, 7.9 Hz, 0.30H), 5.73 (ddd, J = 17.0, 10.0, 8.6 Hz, 0.69H), 5.15 – 4.95 (m, 2H), 3.91 (dd, J = 10.9, 7.9 Hz, 0.29H), 3.79 (dd, J = 10.9, 8.7 Hz, 0.68H), 1.58 – 1.47 (m, 1H), 1.25 (s, 1.65H), 1.24 (s, 1.65H), 1.06 (d, J = 7.3 Hz, 2.05H), 0.98 (s, 4H), 0.95 (s, 4H), 0.82 (d, J = 7.3 Hz, 0.85H). 13C NMR (101 MHz, CDCl3) δ 143.92, 140.46, 132.91, 129.06, 127.55, 127.51, 124.96, 115.77, 83.03, 51.15, 24.50, 24.36, 13.81. 11B NMR (128 MHz, CDCl3) δ 33.63.
HRMS (APCI) calcd for C17 H25O2BBr+ [(M+H)+]:351.1126; found: 351.1126.
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Supporting Information
2-(3-(4-bromophenyl)pent-4-en-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (3d)
Following general procedure B, 3b was used, (45mg, 64%). The product was isolated by flash chromatography (3% ethyl acetate/hexane) as pale yellow oil. 1H NMR (400 MHz, CDCl3) δ 7.42 – 7.33 (m, 2H), 7.15 – 7.02 (m, 2H), 5.98 (ddd, J = 17.2, 10.2, 7.9 Hz, 0.16H), 5.87 – 5.72 (m, 0.84H), 5.09 – 4.93 (m, 2H), 3.28 – 3.15 (m, 1H), 1.41 (dq, J = 10.4, 7.3 Hz, 1H), 1.24 (s, 0.91H), 1.23 (s, 0.91H), 1.03 – 0.99 (m, 12H), 0.77 (d, J = 7.3 Hz, 0.44H). 13C NMR (101 MHz, CDCl3) δ 144.18, 141.44, 131.36, 129.78, 119.84, 115.22, 83.09, 52.71, 24.58, 24.56, 22.82, 13.82. 11B NMR (128 MHz, CDCl3) δ 33.51.
HRMS (APCI) calcd for C17 H25O2BBr+ [(M+H)+]:351.1126; found: 351.1125.
2-(3-(4-fluorophenyl)pent-4-en-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (4d)
Following general procedure B, 8b was used, (44mg, 75%). The product was isolated by flash chromatography (3% ethyl acetate/hexane) as pale yellow oil. 1H NMR (400 MHz, CDCl3) δ 7.22 – 7.10 (m, 2H), 7.00 – 6.90 (m, 2H), 5.99 (ddd, J = 17.1, 10.2, 7.9 Hz, 0.22H), 5.81 (ddd, J = 16.7, 10.3, 8.9 Hz, 0.79H), 5.08 – 4.95 (m, 2H), 3.27 (dd, J = 10.6, 8.0 Hz, 0.20H), 3.24 – 3.16 (m, 0.79H), 1.41 (dq, J = 10.7, 6.8 Hz, 1H), 1.24 (s, 1.13H), 1.23 (s, 1.13H), 1.02 (d, J = 7.3 Hz, 2.5H), 1.00 (s, 9.17H), 0.77 (d, J = 7.3 Hz, 0.58H). 13C NMR (101 MHz, CDCl3) δ 161.48 (d, J = 243.5 Hz),141.93, 140.90 (d, J = 3.1 Hz), 129.35 (d, J = 7.8 Hz), 114.90 (d, J = 7.2 Hz), 115.14, 83.03, 52.61, 24.57, 24.56, 13.94. 11B NMR (128 MHz, CDCl3) δ 33.38. 19F NMR (376 MHz, CDCl3) δ -117.48.
HRMS (APCI) calcd for C17 H25O2BF+ [(M+H)+]:291.1926; found: 291.1940.
Experimental Procedures for Examples Described in Scheme 5. General Procedure C. In air, C4 10 mol% and LiOMe 3 equiv. were added to a Schlenk tube equipped with a stir bar. The vessel was evacuated and filled with argon (three cycles). THF (2.0 mL) was added in turn by syringe under argon atmosphere at room temperature, and then stirred at 60 oC for 15 min. Then gem-diborylalkane (2 or Page S16
Supporting Information 3, 2 equiv.) was added in turn under an argon atmosphere and stirred at 60 oC for 10 min. And allylic epoxides (0.2 mmol) were added in turn under an argon atmosphere. The reaction mixture was stirred at 60 oC for 24 h. The reaction mixture was then diluted with EtOAc, filtered through silica gel with copious washings (Et2O or EtOAc), concentrated, and purified by column chromatography.
5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pent-2-en-1-ol (1e)
Following general procedure C, 1 was used, (28mg, 67%). The product was isolated by flash chromatography (30% ethyl acetate/hexane) as pale yellow oil. And product is a mixture of cis- and trans-((Z)- : (E)- = 1: 4). 1H NMR (400 MHz, CDCl3) δ 5.75 (dt, J = 15.2, 6.2 Hz, 1.2H), 5.62 (m, 1.2H), 4.16 (d, J = 7.1 Hz, 0.5H), 4.07 (dd, J = 5.9, 0.8 Hz, 2H), 2.30 – 2.09 (m, 2.5H), 1.24 (s, 15H), 0.97 – 0.83 (m, 2.5H).13C NMR (101 MHz, CDCl3) δ 135.32, 128.08, 83.23, 64.02, 26.65, 24.97.11B NMR (128 MHz, CDCl3) δ 33.94.
HRMS (APCI) calcd for C11 H22O3B+ [(M+H)+]:213.1657; found: 213.1657.
6-(naphthalen-1-yl)-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)hex-2-en-1-ol (2e)
Following general procedure C, 3 was used, (44mg, 62%). The product was isolated by flash chromatography (30% ethyl acetate/hexane) as pale yellow oil. And product is a mixture of cis- and trans-((Z)- : (E)- = 1: 5.6). 1H NMR (400 MHz, CDCl3) δ 8.05 (d, J = 8.2 Hz, 1H), 7.87 – 7.80 (m, 1H), 7.73 – 7.65 (m, 1H), 7.53 – 7.40 (m, 2H), 7.39 – 7.32 (m, 2H), 5.78 – 5.61 (m, 2.3H), 4.06 (d, J = 4.7 Hz, 2H), 3.23 (dd, J = 14.1, 8.6 Hz, 1H), 3.08 (dd, J = 14.1, 7.4 Hz, 1H), 2.92 (dd, J = 13.7, 8.6 Hz, 0.18H), 2.83 (dd, J = 13.8, 7.8 Hz, 0.18H), 2.33 – 2.17 (m, 2H), 1.70 – 1.55 (m, 1H), 1.17 (s, 6H), 1.12 (s, 6H).13C NMR (101 MHz, CDCl3) δ 137.95, 133.89, 132.51, 132.02, 129.98, 128.67, 126.59, 126.53, 125.64, 125.35, 125.23, 124.13, 83.23, 63.80, 34.07, 33.79, 24.85, 24.73.11B NMR (128 MHz, CDCl3) δ 34.52.
HRMS (APCI) calcd for C22 H29O3BNa+ [(M+Na)+]:375.2102; found: 375.2105.
Experimental of Scheme 6. Page S17
Supporting Information Asymmetric selectivity of the reaction of allylic phosphates with diborylmethane a
General Procedure D. In air, CuCl 10 mol%, LiOMe 3 equiv. and L2-4 13 mol% were added to a Schlenk tube equipped with a stir bar. The vessel was evacuated and filled with argon (three cycles). Dioxane (2.0 mL) was added in turn by syringe under argon atmosphere at room temperature, and then stirred at 60 oC for 15 min. Then diborylmethane (1) was added in turn under an argon atmosphere and stirred at 60 oC for 10 min. And allylic phosphates (0.2 mmol) were added in turn under an argon atmosphere. The reaction mixture was stirred at 60 oC for 24 h. The reaction mixture was then diluted with EtOAc, filtered through silica gel with copious washings (Et2O or EtOAc), concentrated, and purified by column chromatography. And then, the alkylboronic esters were dissolved in 1.0 mL THF, cooled to 0 °C and 2M aq. NaOH (0.25 mL) and 30% aq. H2O2 (0.25 mL) were added simultaneously. The mixture was warmed to RT and stirred for 1 hour. Sat. aq. NH4Cl (2 mL) and Et2O (2 mL) were added and the layers were separated. The aqueous phase was extracted with Et2O (2 × 3 mL) and the combined organics were washed with brine (5 mL), dried (MgSO4), concentrated in vacuo and purified by column chromatography.
2-phenylbut-3-en-1-ol (This compound was previously reported and our spectra data match
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Supporting Information those described, CAS: 6052-63-7 )[4]
Following general procedure D, light yellow oil. The ee was determined on a Daicel Chiralcel AD-H column with hexane/2-propanol = 95/5, flow = 0.5 mL/min. Retention times: 16.6 min [minor enantiomer], 17.4 min [major enantiomer]. 1
H NMR (400 MHz, CDCl3) δ 7.38 – 7.30 (m, 2H), 7.30 – 7.14 (m, 3H), 6.02 (ddd, J = 17.2, 10.4, 7.7
Hz, 1H), 5.32 – 5.08 (m, 2H), 3.82 (dd, J = 7.1, 1.1 Hz, 2H), 3.54 (q, J = 7.3 Hz, 1H), 1.76 (s, 1H). Racemate:
X= pinacol, L2
X= pinacol, L3
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Supporting Information
X= pinacol, L4
X= pinanediol, L3
X= pinanediol, L4
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Supporting Information
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Supporting Information IV. References [1] Semba, K.; Bessho, N.; Fujihara, T.; Terao, J.; Tsuji, Y. Angew. Chem. Int. Ed. 2014, 53, 9007. [2] Zhang, Z.-Q.; Yang, C.-T.; Liang, L.-J.; Xiao, B.; Lu, X.; Liu, J.-H.; Sun, Y.-Y.; Marder, T. B.; Fu, Y. Org. Lett. 2014, 16, 6342. [3] Shintani, R.; Takatsu, K.; Hayashi, T. Chem. Commun. 2010, 46, 6822. [4] Yu, B.; Menard, F.; Isono, N.; Lautens, M. Synthesis 2009, 2009, 853.
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Supporting Information Ⅴ. NMR Spectra and GC-MS Analysis 1
H NMR, 13C NMR and 11B NMR of 2-(2-(2-bromophenyl)but-3-en-1-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (2c)
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Supporting Information
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Supporting Information 1
H NMR, 13C NMR and 11B NMR of 2-(2-(4-bromophenyl)but-3-en-1-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (3c)
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Supporting Information
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Supporting Information 1
H NMR, 13C NMR and 11B NMR of 2-(2-(2-chlorophenyl)but-3-en-1-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (4c)
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Supporting Information
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Supporting Information 1
H NMR, 13C NMR and 11B NMR of 2-(2-(3-chlorophenyl)but-3-en-1-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (5c)
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Supporting Information
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Supporting Information 1
H NMR, 13C NMR and 11B NMR of 2-(2-(4-chlorophenyl)but-3-en-1-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (6c)
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Supporting Information
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Supporting Information 1
H NMR, 13C NMR and 11B NMR of
4,4,5,5-tetramethyl-2-(2-(4-nitrophenyl)but-3-en-1-yl)-1,3,2-dioxaborolane (7c)
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Supporting Information
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Supporting Information 1
H NMR, 13C NMR 11B NMR and 19F NMR of 2-(2-(4-fluorophenyl)but-3-en-1-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (8c)
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Supporting Information
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Supporting Information 1
H NMR, 13C NMR 11B NMR and 19F NMR of 4,4,5,5-tetramethyl-2-(2-(3-(trifluoromethyl)phenyl)but-3-en-1-yl)-1,3,2-dioxaborolane (9c)
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Supporting Information
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Supporting Information 1
H NMR, 13C NMR and 11B NMR of
4-(1-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)but-3-en-2-yl)benzonitrile (10c)
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Supporting Information
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Supporting Information 1
H NMR, 13C NMR and 11B NMR of
4,4,5,5-tetramethyl-2-(2-vinylpentyl)-1,3,2-dioxaborolane (11c)
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Supporting Information
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Supporting Information 1
H NMR, 13C NMR and 11B NMR of (Z)-4,4,5,5-tetramethyl-2-(2-vinyloct-5-en-1-yl)-1,3,2-dioxaborolane (13c)
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Supporting Information
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Supporting Information 1
H NMR, 13C NMR and 11B NMR of
2-((4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)methyl)but-3-en-1-yl benzoate (14c)
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Supporting Information
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Supporting Information 1
H NMR, 13C NMR and 11B NMR of 2-((4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)methyl)but-3-en-1-yl thiophene-2-carboxylate (15c)
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Supporting Information
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Supporting Information 1
H NMR, 13C NMR and 11B NMR of 2-((4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)methyl)but-3-en-1-yl furan-2-carboxylate (16c)
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Supporting Information
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Supporting Information 1
H NMR, 13C NMR and 11B NMR of 2-(2-((benzyloxy)methyl)but-3-en-1-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (17c)
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Supporting Information
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Supporting Information 1
H NMR, 13C NMR and 11B NMR of tert-butyldimethyl((2-((4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)methyl)but-3-en-1-yl)ox y)silane (18c)
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Supporting Information
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Supporting Information 1
H NMR, 13C NMR and 11B NMR of (E)-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pent-2-en-1-yl benzoate (19c)
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Supporting Information
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Supporting Information 1
H NMR, 13C NMR and 11B NMR of 2-(2,2-dimethylbut-3-en-1-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (20c)
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Supporting Information
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Supporting Information 1
H NMR, 13C NMR and 11B NMR of 4,4,5,5-tetramethyl-2-(3-phenylpent-4-en-2-yl)-1,3,2-dioxaborolane (1d)
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Supporting Information
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Supporting Information 1
H NMR, 13C NMR and 11B NMR of 2-(3-(2-bromophenyl)pent-4-en-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (2d)
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Supporting Information
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Supporting Information 1
H NMR, 13C NMR and 11B NMR of 2-(3-(4-bromophenyl)pent-4-en-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (3d)
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Supporting Information
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Supporting Information 1
H NMR, 13C NMR and 19F NMR of 2-(3-(4-fluorophenyl)pent-4-en-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (4d)
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Supporting Information
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Supporting Information 1
H NMR, 13C NMR and 11B NMR of 5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pent-2-en-1-ol (1e)
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Supporting Information
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Supporting Information 1
H NMR, 13C NMR and 11B NMR of 6-(naphthalen-1-yl)-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)hex-2-en-1-ol (2e)
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Supporting Information
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Supporting Information 1
H NMR, 13C NMR and 11B NMR of 2-phenylbut-3-en-1-ol
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