Electronic Supplementary Information Pd-Catalyzed Hydroborylation of Alkynes: A Ligand Controlled Regioselectivity Switch for the Synthesis of α- or β-vinylboronates Devi Prasan Ojha and Kandikere Ramaiah Prabhu* Department of Organic Chemistry, Indian Institute of Science, Bangalore560 012, Karnataka, India Table of Contents General Information General procedure for the synthesis of IPr-Hcl General Procedures for α-borylation of terminal alkynes General Procedures for β-borylation of terminal alkynes Regioselective borylation of hex-5-ynenitrile using MeOD Control experiments with different oxidizing agents for borylation Competitive experiments Characterization References NMR Spectra noe Exoeriment (2f ) SI-2 SI-2 SI-2 SI-2 SI-3 SI-3 SI-3 SI-4 SI-9 SI-10 SI-46
General Information All solvents were distilled under nitrogen atmosphere prior to use. 1, 4-Dioxane, toluene were dried over Na. Unless otherwise noted, commercially available chemicals were distilled and degassed before use. Palladium acetate (II) trimer (CAS:3375-31-3) was used for the reaction, For chromatography, 200-300 mesh silica gel was employed. 1 H spectra were recorded at 400 MHz and 500 MHz and 13 C NMR spectra were recorded at 100 MHz and 125 MHz spectrometer. Chemical shifts ( 1 H) are reported in ppm using tetramethylsilane as internal standard when CDCl 3 was used as solvent. For 13 C NMR, the triplet of CDCl 3 (the center peak at δ 77.00) is used as reference. IR spectra were recorded using Perkin Elmer FT-IR instrument. Mass spectra (EI) were recorded using Shimadzu QP-2010 Ultra and High resolution mass spectra (HRMS) were recorded on Q-TOF (Micromass) spectrometer. General procedure for the synthesis of IPr-Hcl 1 A dilute solution of HCl (69 ml of 4 M solution in dioxane) was added into a well-stirred solution of diazabutadiene ((1E,2E)-N1,N2-bis(2,6-diisopropylphenyl)ethane-1,2-diimine) (3.76 g, 10 mmol) in 37 ml of ethyl acetate (0.5 M), followed by addition of paraformaldehyde (6.1 g, 0.2 mol). The reaction mixture was stirred at room temperature till the reaction mixture becomes homogeneous (~1h). (Paraformaldehyde solution should be added to the solution of diazabutadiene to maintain a gentle heating without reaching reflux of the solvent (1 h)). The reaction mixture was stirred overnight at room temperature while the yellow colored reaction mixture turns to brown. The precipitate formed during the reaction was filtered and washed with ethyl acetate (3 100 ml). After drying of the precipitate under vacuum (16 h), the product was obtained as an off-white solid. The solid was dissolved in a saturated aqueous solution of NaHCO 3 and transferred into a separating funnel, washed with ethyl acetate (3 100 ml), followed CH 2 Cl 2 (3 100 ml). The combined organic phase was dried over MgSO 4 (20 30 g and manually stirred for 1 min), filtered and concentrated under vacuum with a rotary evaporator (pressure 580 mbar with a water bath temperature at 40 C). Recrystallized using a mixture of ethyl acetate and CH 2 Cl 2 (450 ml, 8:1). Filter the white precipitate and wash it three times with ethyl acetate (3 50 ml). Dry the product under vacuum. General Procedures for α-borylation of terminal alkynes To an oven-dried Teflon capped vial equipped with a magnetic stirring bar were added sequentially bromobenzene (187 mg, 1mmol), bis(pinacolato)diboron ( 278 mg, 1.1 mmol), PCy 3 (28 mg, 0.10 mmol), [Pd(OAc) 2 ] 3 (4.0 mg, 0.05 mmol), alkyne (1 mmol), toluene (2 ml) and trifluoroethanol (2 mmol) under argon. The mixture was stirred at 80 ºC for 12 h (monitored by TLC). Upon completion of the reaction, the resulting mixture was filtered through a short column of silica gel (eluted with Et 2 O, 20 ml 3) and concentrated. This crude mixture was further purified on a silica gel column chromatography to obtain pure product. General Procedures for β-borylation of terminal alkynes To an oven-dried Teflon capped vial equipped with a magnetic stirring bar were added sequentially bromobenzene (187 mg, 1 mmol), bis(pinacolato)diboron ( 278 mg, 1.1 mmol), IPr- HCl (5 mmol%), t BuOK (11 mol%), [Pd(OAc) 2 ] 3 ( 4.0mg, 0.025 mmol), alkyne (1 mmol), toluene (2 ml) and trifluoroethanol (2 mmol) under argon. The mixture was stirred at 80 ºC for 12 h (monitored by TLC). Upon completion of the reaction, the resulting mixture was filtered through a short column of silica gel (eluted with Et 2 O, 20 ml 3) and concentrated. This crude mixture was further purified on a silica gel column chromatography to obtain pure product. SI - 2
Regioselective borylation of hex-5-ynenitrile using MeOD Following the general procedure described above, (E)-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan- 2-yl)hex-5-enenitrile-6-d was obtained as a colourless liquid, 62.4 mg (71%, 60% 2 H insertion). 1 H NMR (CDCl 3, 300 MHz): δ 1.26 (s, 12H), 1.77-1.84 (m, 2H), 2.14 (q, J= 7.2 Hz, 4H), 5.66 (s, 1H), 5.86 (d, J= 2.8 Hz, 1H,); 13 C NMR (CDCl 3 ): δ 16.4, 24.7, 24.98, 34.3, 83.5, 131.1. The stereochemistry was confirmed by a 1D - noe experiment of the non-=deuterated product. Control experiments with different oxidizing agents for borylation Competitive experiments Entry Oxidants (1.1 equiv) yields 1 PIDA 10 % 2 PIFA 15 % 3 MeI nr 4 BQ nr To an oven-dried Teflon capped vial equipped with a magnetic stirring bar were added sequentially bromobenzene (187 mg, 1mmol), bis(pinacolato)diboron ( 278 mg, 1.1 mmol), PCy 3 (28 mg, 0.10 mmol), [Pd(OAc) 2 ] 3 (4.0 mg, 0.05 mmol), alkynes 1g (0.5 mmol) and 1f (0.5 mmol) were subjected for a competitive hydroborylation in toluene (2 ml) and trifluoroethanol (2 mmol) under argon. The mixture was stirred at 80 ºC for 12 h (monitored by TLC). Upon completion of the reaction, the resulting mixture was filtered through a short column of silica gel (eluted with Et 2 O, 20 ml 3) and concentrated. This reaction resulted in distinguishable borylated products 2f and 2g in 70:30 ratios and the conversion was obtained by 1 H-NMR spectra (see spectral section below). SI - 3
Characterization 4,4,5,5-tetramethyl-2-(1-phenylvinyl)-1,3,2-dioxaborolane: 1 Purified by flash chromatography on silica gel using EtOAc: hexane (1:10) as eluent. R f (hexane) = 0.5. off-white solid; Yield: 41%, (1.74 g); IR (neat, cm 1 ): 3105, 2989, 1521, 1461, 1454, 1168, 1065, 1038; 1 H NMR (CDCl 3, 400 MHz): δ 10.1 (s, 1H), 8.13 (s, 2H), 7.57 (t, J= 7.6 Hz, 2H), 7.35 (d, J= 8.0 Hz, 4H), 2.45 (pent, J= 6.8 Hz, 4H), 1.29 (d, J= 6.8 Hz, 12H), 1.24 (d, J= 6.8 Hz, 12H); 13 C NMR (CDCl 3 ): δ 24.2, 28.4, 124.3, 125.5, 128.9, 142.8; HRMS (ESI) : calculated for C 27 H 37 ClN 2 : 424.2645; Found: 424.2648.The physical data were identical to those previously reported data. 4,4,5,5-tetramethyl-2-(non-1-en-2-yl)-1,3,2-dioxaborolane): 2 2a O B O Purified by flash chromatography on silica gel using EtOAc : hexane (1:10) as eluent. R f (hexane) = 0.5. Colourless liquid; Yield: 85%, (214 mg); IR (neat, cm 1 ): 3452, 2959, 1598, 1454, 1065; 1 H NMR (CDCl 3, 400 MHz): δ 0.87-0.89 (m, 3H), 1.26 (s, 20H), 1.39-1.42 (m, 2H), 2.14 (t, J= 7.2 Hz, 2H), 5.58 (s, 1H), 5.74 (d, J = 2.8 Hz, 1H,); 13 C NMR (CDCl 3 ): δ 14.1, 22.6, 24.7, 24.8, 29.19, 29.2, 31.8, 35.3, 83.2, 128.6; MS (m/z) (rel. intensity): 252 (11), 237 (73), 153 (100). The physical data were identical to those previously reported data. 4,4,5,5-tetramethyl-2-(oct-1-en-2-yl)-1,3,2-dioxaborolane): 3 Purified by flash chromatography on silica gel using EtOAc : hexane (1:10) as eluent. R f (hexane) = 0.5. Colourless liquid; Yield: 73%, (173 mg); IR (neat, cm 1 ): 3467, 2928, 2617, 1362, 1318; 1 H NMR (CDCl 3, 400 MHz): δ 0.87-0.89 (m, 3H), 1.26 (s, 19H), 1.39-1.42 (m, 2H), 2.14 (t, J= 7.2 Hz, 2H), 5.59 (s, 1H), 5.75 (d, J= 2.8 Hz, 1H,); 13 C NMR (CDCl 3 ): δ 14.1, 22.6, 24.7, 29.19, 29.2, 31.8, 35.3, 83.2, 128.6; MS (m/z) (rel. intensity): 238 (10), 223 (53), 153 (100). The physical data were identical to those previously reported data. SI - 4
2-(hept-1-en-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane: 4 Purified by flash chromatography on silica gel using EtOAc : hexane (1:10) as eluent. R f (hexane) = 0.5. Colourless liquid; Yield: 69%, (154 mg); IR (neat, cm 1 ): 3658, 2974, 2927, 1638, 1462; 1 H NMR (CDCl 3, 400 MHz): δ 5.75 (d, J= 2.8 Hz, 1H), 5.59 (s, 1H), 2.13 (t, J= 7.6 Hz, 2H), 1.42-1.37 (m, 2H), 1.26 (m, 18H), 0.88-0.86 (m, 3H); 13 C NMR (CDCl 3 ): δ 14.0, 22.5, 24.7, 24.8, 28.8, 31.4, 35.2, 83.2, 128.6; MS (m/z) (rel. intensity): 224 (11), 209 (53), 153 (100). The physical data were identical to those previously reported data. 2-(hex-1-en-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane: 3 Purified by flash chromatography on silica gel using EtOAc : hexane (1:10) as eluent. R f (hexane) = 0.5. Colourless liquid; Yield: 65%, (136 mg); IR (neat, cm 1 ): 3429, 2989, 1557, 1479, 1444, 1168, 1015; 1 H NMR (CDCl 3, 400 MHz): δ 0.87-0.89 (m, 3H), 1.26 (s, 13H), 1.36-1.43 (m, 4H), 2.14 (t, J= 7.2 Hz, 2H), 5.58 (s, 1H), 5.75 (d, J= 2.8 Hz, 1H); 13 C NMR (CDCl3): δ 14.1, 22.3, 24.7, 31.4, 35.0, 83.2, 128.5; MS (m/z) (rel. intensity): 210 (12), 195 (59), 153 (100). The physical data were identical to those previously reported data. 4,4,5,5-tetramethyl-2-(pent-1-en-2-yl)-1,3,2-dioxaborolane: 5 Purified by flash chromatography on silica gel using EtOAc : hexane (1:10) as eluent. R f (hexane) = 0.5. Colourless liquid; Yield: 55%, (107 mg); IR (neat, cm 1 ): 3412, 2939, 1587, 1478, 1457, 1169, 1055, 1028; 1 H NMR (CDCl 3, 400 MHz): δ 0.87-0.89 (m, 3H), 1.26 (s, 12H), 1.41-1.46 (m, 2H), 2.12 (t, J= 7.2 Hz, 2H), 5.59 (s, 1H), 5.76 (d, J= 2.8 Hz, 1H,); 13 C NMR (CDCl 3 ): δ 13.7, 22.3, 24.7, 37.5, 83.2, 128.89; MS (m/z) (rel. intensity): 196 (21), 181 (40), 139 (100). The physical data were identical to those previously reported data. 5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)hex-5-enenitrile: 6 Purified by flash chromatography on silica gel using EtOAc : hexane (1:10) as eluent. R f (hexane) = 0.5. Colourless liquid; Yield: 89%, (189 mg); IR (neat, cm 1 ): 3022, 2269, 1587, 1068, 1065, 938; 1 H NMR (CDCl 3, 400 MHz): δ 1.26 (s, 12H), 1.77-1.84 (m, 2H), 2.14 (q, J= 7.2 Hz, 4H), 5.66 (s, 1H), 5.86 (d, J= 2.8 Hz, 1H,); 13 C NMR (CDCl3): δ 16.4, 24.7, 24.98, 34.3, SI - 5
83.5, 131.1; MS (m/z) (rel. intensity): 220 (9), 206 (33), 135 (100). The physical data were identical to those previously reported data. 4,4,5,5-tetramethyl-2-(1-(p-tolyl)vinyl)-1,3,2-dioxaborolane: Purified by flash chromatography on silica gel using hexane as eluent. R f (hexane) = 0.5. Colourless oil; Yield: 93%, (280 mg); IR (neat, cm 1 ): 3462, 2959, 1567, 1473, 1451, 1178, 1095, 1018; 1 H NMR (CDCl 3, 400 MHz): δ 7.37 (d, J= 7.6 Hz, 2H), 7.12 (d, J= 7.6 Hz, 2H), 6.0 (m, 2H), 2.32 (s, 3H), 1.31 (s, 12H); 13 C NMR (CDCl 3 ): δ 136.6, 129.9, 128.9, 127.0, 124.7, 3.7, 24.7, 21.1; HRMS (ESI) : calculated for C 15 H 21 BO 2 Na : 267.1532; Found: 267.1552. 4,4,5,5-tetramethyl-2-(3-phenoxyprop-1-en-2-yl)-1,3,2-dioxaborolane: 5 Purified by flash chromatography on silica gel using EtOAc : hexane (1:10) as eluent. R f (hexane) = 0.5. Colourless liquid; Yield: 62%, (161 mg); IR (neat, cm 1 ): 3431, 2980, 2670, 2336, 2107, 1826, 1347, 1315, 1143; 1 H NMR (CDCl 3, 400 MHz): δ 7.28-7.24 (m, 3H), 6.94-6.90 (m, 2H), 6.02 (d, J= 10 Hz, 2H), 4.6 (s, 2H), 1.28 (s, 12H); 13 C NMR (CDCl 3 ): δ 24.7, 69.1, 88.3, 83.6, 114.6, 117.2, 120.5, 129.2, 129.4, 129.5, 129.8, 158.7; MS (m/z) (rel. intensity): 260 (51), 245 (53), 175 (100), 133 (15), 93 (29). The physical data were identical to those previously reported data. 2-(3-(((3S,8S,9S,10R,13S,14R,17R)-10,13-dimethyl-17-((R)-6-methylheptan-2-yl)- 2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydro-1H-cyclopenta[a]phenanthren-3- yl)oxy)prop-1-en-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane: Purified by flash chromatography on silica gel using EtOAc : hexane (1:10) as eluent. R f (hexane) = 0.5. Colourless liquid; Yield: 41%, (226 mg); IR (neat, cm 1 ): 3402, 2939, 1567, 1484, 1400, 1168, 1065, 1038; 1 H NMR (CDCl 3, 400 MHz): 0.67 (s, 8H), 0.5-0.87 (m, 8H), 0.9-1.00 (m, 6H), 1.10-1.11 (m, 5H), 1.26 (s, 12H), 1.34-1.48 (m, 12H), 1.82-1.99 (m, 6H), 3.2 (m, SI - 6
1H), 4.13 (s, 2H), 5.33 (s, 1H), 5.91 (m, 2H); 13 C NMR (CDCl 3 ): δ 11.8, 18.7, 19.3, 21.0, 22.5, 23.8, 24.27, 24.84, 27.99, 28.2, 29.69, 31.9, 35.7, 36.1, 36.8, 39.7, 42.2, 50.15, 56.1, 56.7, 69.4, 83.17, 128.2, 129.0, 130.0, 131.5; MS (m/z) (rel. intensity): 551, 441 (100). (Our attempts to record HRMS for this sample was not successful). 2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)allyl 2-phenylacetate: Purified by flash chromatography on silica gel using EtOAc: hexane (1:10) as eluent. R f (hexane) = 0.5. Colourless liquid; Yield: 93%, (280 mg); IR (neat, cm 1 ): 3462, 2959, 1567, 1473, 1451, 1178, 1095, 1018; 1 H NMR (CDCl 3, 400 MHz): δ 7.35-7.14 (m, 11H), 6.6 (dt, J= 18 Hz, J= 4.8 Hz, 1.3H), 5.9 (s, 1H), 5.75 (s, 1H), 5.65 (d, J= 18 Hz, 1.3 H), 4.72 (s, 2H), 4.67 (d, J3.6 Hz, 2.8H), 3.66 (s, 5H), 1.26 (s, 15H), 1.24 (s, 12H); 13 C NMR (CDCl3): δ 24.6, 24.7, 41.4, 41.4, 65.8, 66.3, 83.4, 83.67, 126.9, 127.4, 128.4, 128.5, 129.2, 130.0, 130.1, 133.7, 134.0, 145.7, 171.0; HRMS (ESI) : calculated for C 17 H 23 BO 4 Na : 325.1668; Found: 325.1672. 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pent-4-en-1-ol: 7 Purified by flash chromatography on silica gel using EtOAc : hexane (1:10) as eluent. R f (hexane) = 0.5. Colourless liquid; Yield: 63%, (133 mg); IR (neat, cm 1 ): 3409, 2335, 2106, 1887; 1 H NMR (CDCl 3, 400 MHz): δ 6.64 (dt, J 1 = 18 Hz, J 2 = 6.8, 1H), 6.3-6.29 (m, 1H), 5.47 (d, J= 18 Hz, 1H), 3.71 (t, J= 6.8 Hz, 2H), 3.66 (t, J= 6.8 Hz, 2H), 2.43 (q, J= 6.4 Hz, 2H), 2.25 (q, J= 7.2 Hz, 2H), 1.72-1.69 (m, 6H), 1.26 (s, 24H); 13 C NMR (CDCl3): δ 14.09, 24.7, 24.79, 29.6, 13.1, 31.9, 32.2, 61.8, 62.4, 83.2, 141.2, 153.5; MS (m/z) (rel. intensity): MS (m/z) (rel. intensity): 212 (5), 197 (23), 152 (21), 69 (90), 101 (70), 41(100). The physical data were identical to those previously reported data. (Z)-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)but-2-en-1-ol: 8 HO 2l O B O Purified by flash chromatography on silica gel using EtOAc : hexane (1:10) as eluent. R f (hexane) = 0.5. Colourless liquid; Yield: 71%, (140 mg); IR (neat, cm 1 ): 3422, 2969, 1597, 1454, 1168, 1065; 1 H NMR (CDCl 3, 400 MHz): δ 6.38 (m, 1H), 4.51 (d, J= 5.6 Hz, 2H), 1.68 (s, 3H), 1.27 (s, 12H); 13 C NMR (CDCl 3 ): δ 142.9, 83.0, 62.1, 24.4, 14.1; MS (m/z): 310 & 184; The physical data were identical to those previously reported data. SI - 7
(E)-4,4,5,5-tetramethyl-2-(non-1-en-1-yl)-1,3,2-dioxaborolane: 3a O B O Purified by flash chromatography on silica gel using EtOAc : hexane (1:10) as eluent. R f (hexane) = 0.5. yellow liquid; Yield: 80%, (201 mg); IR (neat, cm 1 ): 3392, 2979, 1591, 1478, 1458, 1188, 1068, 1088; 1 H NMR (CDCl 3, 400 MHz): δ 0.85-0.89 (m, 3H), 1.26 (s, 12H), 1.22-1.34 (10H, m), 1.36-1.44 (m, 2H), 2.15 (q, J = 8.1 Hz, 2H), 5.42 (d, J = 18.8 Hz, 1H), 6.63 (dt, J = 18.8, 8.1 Hz, 1H,). 13 C NMR (CDCl 3, 125 MHz) δ = 14.1, 22.6, 24.7, 28.2, 29.1, 29.18, 31.79, 35.8, 82.9, 154.88; MS (m/z) (rel. intensity): 252 (11), 237 (73), 153 (100). (Our attempts to record HRMS for this sample was not successful) (E)-4,4,5,5-tetramethyl-2-(oct-1-en-1-yl)-1,3,2-dioxaborolane: 9 Purified by flash chromatography on silica gel using EtOAc : hexane (1:10) as eluent. R f (hexane) = 0.5. pale yellow liquid; Yield: 76%, (180 mg); IR (neat, cm 1 ): 3467, 2928, 2617, 1362, 1318; 1 H NMR (CDCl 3, 400 MHz): δ 0.86-0.89 (m, 3H), 1.26 (m, 12H), 1.22-1.34 (m, 8H), 1.39-1.41 (m, 2H), 2.15 (q, J= 6.4 Hz, 2H), 5.42 (d, J= 18 Hz, 1H,), 6.63 (dt, J= 18.8, 8.1 Hz, 1H). 13 C NMR (CDCl 3, 125 MHz) δ = 14.0, 22.5, 24.7, 28.1, 28.8, 31.6, 35.8, 82.9, 154.8; MS (m/z) (rel. intensity): 238 (10), 223 (53), 153 (100). The physical data were identical to those previously reported data. (E)-2-(hept-1-en-1-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane: 4 Purified by flash chromatography on silica gel using EtOAc : hexane (1:10) as eluent. R f (hexane) = 0.5. yellow liquid; Yield: 85%, (190 mg); IR (neat, cm 1 ): 3658, 2974, 2927, 1638, 1462; 1 H NMR (CDCl 3, 400 MHz): δ 0.86-0.89 (m, 3H), 1.26 (s, 16H), 1.39-1.43 (m, 2H), 2.14 (q, J= 7.2 Hz, 2H), 5.42 (d, J= 18 Hz, 1H), 6.63 (dt, J= 18 Hz, 1H); 13 C NMR (CDCl 3 ): δ 13.9, 22.5, 24.7, 27.8, 31.3, 35.7, 82.9, 154.8; MS (m/z) (rel. intensity): 224 (11), 209 (53), 153 (100). The physical data were identical to those previously reported data. (E)-4,4,5,5-tetramethyl-2-styryl-1,3,2-dioxaborolane: 4 3d O B O Purified by flash chromatography on silica gel using EtOAc : hexane (1:10) as eluent. R f (hexane) = 0.5. Colourless liquid; Yield: 81%, (186 mg); IR (neat, cm 1 ): 3411, 2973, 1576, SI - 8
1479, 1458, 1171, 1043, 1041; 1 H NMR (CDCl 3, 400 MHz): δ 1.31 (s, 12H,), 6.17 (1H, d, J= 18.8 Hz). 13 C NMR (CDCl3, 125 MHz) δ = 24.7, 83.3, 127.0, 128.5, 128.8, 137.4, 149.4; MS (m/z) (rel. intensity): 230 (51), 215 (53), 146 (100), 103 (91). The physical data were identical to those previously reported data. References: (1) Hintermann, L.; Beilstein J. Org. Chem. 2007, 3: 22; (b) Arduengo, A. J.; Krafczyk, R.; Schmutzler, R.; Craig, H. A.; Goerlich, J. R.; Marshall, W. J.; Unverzagt, M. Tetrahedron 1999, 55, 14523 14534. (c) Bantreil, X.; Nolan, S. P. Nat. Prot. 2011, 6, 69-77. (2) Yuan, W.; Ma, S. Adv. Syn. Cat. 2012, 354, 1867 1872. (3) Ganic, A.; Pfaltz, A. Chem. -A Eur. J. 2012, 18, 6724 6728. (4) Coombs, J. R.; Zhang, L.; Morken, J. P. Org. Lett. 2015, 17, 1708 1711. (5) Moure, A. L.; Mauleón, P.; Arrayás, R. G.; Carretero, J. C. Org. Lett. 2013, 15, 2054-2057. (6) Jun, T.; Kou, T.; Tatsuo, I.; Miyaura, N. J. Am. Chem. Soc. 2002, 124, 8001 8006. (7) Jang, H.; Zhugralin, A. R.; Lee, Y.; Hoveyda, A. H. J. Am. Chem. Soc. 2011, 133, 7859 7871. (8) Moure, A. L.; Arrayás, R. G.; Cárdenas, D. J.; Alonso, I.; Carretero, J. C. J. Am. Chem. Soc. 2012, 134, 7219-7222. (9) Takaya, J.; Kirai, N.; Iwasawa, N. J. Am. Chem. Soc. 2011, 133, 12980-12983 SI - 9
10 9 8 7 6 5 4 3 2 1 0 ppm 0.922 1.929 3.980 1.998 4.000 24.105 10.092 7.271 7.341 7.361 7.554 7.574 7.593 8.136 1.237 1.254 1.280 1.297 1.804 2.415 2.432 2.449 2.466 2.483 0.000 SI - 10
142.808 124.388 125.537 128.954 76.682 77.000 77.318 24.199 28.407 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm SI - 11
10 9 8 7 6 5 4 3 2 1 0 ppm 0.963 1.000 2.402 21.310 2.527 3.722 7.264 5.587 5.746 5.753 0.859 0.876 0.889 1.267 1.390 1.402 1.420 2.117 2.135 2.153-0.000 SI - 12
128.657 76.682 77.000 77.317 83.269 14.115 22.669 24.724 24.787 29.195 29.227 31.847 35.333 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm SI - 13
10 9 8 7 6 5 4 3 2 1 0 ppm 0.210 0.257 1.007 1.000 2.840 19.763 2.088 3.349 5.405 5.449 5.591 5.750 5.758 6.601 6.618 6.634 6.646 6.663 6.679 7.268 0.862 0.879 0.895 1.271 1.353 1.393 1.406 1.426 2.108 2.120 2.139 2.157 0.004 SI - 14
128.658 76.684 77.001 77.319 83.270 14.116 22.670 24.726 29.197 29.229 31.849 35.335 2b B O O 13 CNMR100MHzCDCl3 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm SI - 15
7.263 5.588 5.747 5.754 0.861 0.878 0.893 1.267 1.374 1.392 1.411 1.427 2.116 2.135 2.154-0.000 2c B O O 1 HNMR400MHzCDCl3 10 9 8 7 6 5 4 3 2 1 0 ppm 1.024 1.000 2.478 18.466 2.402 3.451 SI - 16
128.652 76.682 77.000 77.317 83.260 14.042 22.565 24.718 24.812 28.855 31.473 35.292 2c B O O 13 CNMR100MHzCDCl3 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm SI - 17
10 9 8 7 6 5 4 3 2 1 0 ppm 0.981 1.000 2.305 13.058 4.138 3.205 7.263 5.590 5.749 5.755 2.125 2.144 2.161 0.874 0.884 0.892 1.268-0.000 SI - 18
SI - 19
5.591 5.763 5.770 0.000 0.871 0.889 0.908 1.266 1.392 1.410 1.429 1.448 1.466 2.104 2.123 2.142 2e B O O 1 HNMR400MHzCDCl3 10 9 8 7 6 5 4 3 2 1 0 ppm 0.923 1.000 2.143 12.034 2.174 3.243 SI - 20
128.893 76.683 77.000 77.318 83.234 37.505 22.325 24.702 13.775 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm SI - 21
10 9 8 7 6 5 4 3 2 1 0 ppm 0.983 1.000 4.066 2.131 12.494 7.271 5.671 5.861 5.867 1.266 1.776 1.795 1.813 1.831 1.849 2.272 2.294 2.313 2.332 0.000 SI - 22
131.137 119.854 76.683 77.000 77.318 83.558 34.319 24.722 24.986 16.426 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm SI - 23
10 9 8 7 6 5 4 3 2 1 0 ppm 2.675 2.279 2.000 3.433 12.464 7.114 7.133 7.258 7.365 7.384 6.001 6.040 2.329 1.318 1.551 0.000 SI - 24
124.752 127.047 128.882 129.983 136.670 76.683 77.001 77.318 83.730 21.101 24.789 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm SI - 25
10 9 8 7 6 5 4 3 2 1 0 ppm 3.356 3.528 0.325 2.000 0.730 2.007 4.778 12.151 6.922 6.942 7.245 7.263 5.808 5.854 6.012 6.037 4.607 4.614 4.647 1.269 1.282 0.000 SI - 26
158.758 114.621 114.884 117.237 120.511 129.276 129.400 129.530 129.855 69.139 76.682 77.000 77.318 83.365 83.662 24.736 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm SI - 27
10 9 8 7 6 5 4 3 2 1 0 ppm 2.000 1.389 1.950 1.380 6.286 8.160 8.214 6.109 5.180 12.095 12.408 7.261 5.898 5.933 5.336 4.131 0.675 0.857 0.873 0.907 0.921 1.001 1.101 1.116 1.266 1.348 1.486 1.577 1.827 1.896 1.949 1.991 3.202 SI - 28
128.203 129.013 130.014 131.515 11.841 18.700 19.368 21.047 22.552 22.813 23.807 24.271 24.747 24.849 27.999 28.226 29.695 31.921 35.774 36.169 36.860 39.497 39.766 42.298 50.159 56.124 56.761 69.415 76.683 77.000 77.318 83.174 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0-10 ppm SI - 29
10 9 8 7 6 5 4 3 2 1 0 ppm 11.890 1.283 1.379 1.014 1.000 2.780 2.145 5.142 12.518 15.300 5.648 5.693 5.755 5.903 6.569 6.580 6.592 6.614 6.626 6.637 4.669 4.678 4.721 3.660 1.246 1.268 0.000 SI - 30
171.087 126.981 127.098 128.483 128.554 129.275 130.006 130.131 133.754 134.088 145.703 65.847 66.313 76.683 77.000 77.318 83.407 83.674 41.166 41.433 24.695 24.732 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm SI - 31
10 9 8 7 6 5 4 3 2 1 0 ppm 1.000 1.130 1.036 1.775 2.249 1.878 2.388 6.136 13.102 6.291 6.308 6.605 6.621 6.637 6.649 6.666 7.263 5.452 5.497 1.249 1.691 1.707 1.725 2.224 2.240 2.258 2.411 2.427 2.443 2.460 3.646 3.663 3.679 3.703 3.719 3.735-0.000 SI - 32
153.506 141.282 76.683 77.000 77.318 83.080 83.273 61.877 62.418 14.096 24.761 24.795 29.683 31.144 31.967 32.203 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm SI - 33
7.283 6.381 6.525 6.543 6.560 6.577 5.696 4.509 4.523 1.686 1.272-0.000 10 9 8 7 6 5 4 3 2 1 0 ppm 0.993 1.781 2.268 2.974 13.609 SI - 34
142.891 76.683 77.000 77.318 83.053 62.177 24.447 14.108 220 200 180 160 140 120 100 80 60 40 20 0 ppm SI - 35
10 9 8 7 6 5 4 3 2 1 0 ppm 0.979 1.000 0.181 0.184 2.562 21.766 2.328 3.383 5.400 5.445 5.586 5.745 6.597 6.613 6.629 6.642 6.658 6.674 0.858 0.875 0.890 1.266 1.392 1.408 1.422 1.577 2.117 2.135 2.152 2.169 0.000 SI - 36
154.887 76.683 77.001 77.318 82.969 14.092 22.653 24.760 28.210 29.151 29.188 31.791 35.829 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm SI - 37
10 9 8 7 6 5 4 3 2 1 0 ppm 1.001 1.000 2.162 18.362 2.083 3.211 6.584 6.600 6.616 6.628 6.644 6.660 7.267 5.387 5.432 0.846 0.849 0.862 0.876 1.251 1.379 1.396 1.745 2.106 2.123 2.141 2.157-0.014 SI - 38
154.804 76.682 76.999 77.317 82.911 14.056 22.558 24.726 28.148 28.878 31.683 35.805 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm SI - 39
6.599 6.615 6.631 6.644 6.660 6.676 7.268 5.401 5.446 0.860 0.877 0.893 1.266 1.397 1.415 1.432 1.628 2.117 2.135 2.152 2.169-0.001 3c B O O 1 HNMR400MHzCDCl3 10 9 8 7 6 5 4 3 2 1 0 ppm 0.992 1.000 2.323 15.007 2.205 3.366 SI - 40
154.856 76.682 77.000 77.318 82.958 22.503 24.756 27.877 31.392 35.778 13.989 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm SI - 41
10 9 8 7 6 5 4 3 2 1 0 ppm 3.128 1.231 2.118 1.000 12.059 6.150 6.197 7.210 7.218 7.280 7.297 7.312 7.330 7.348 7.380 7.426 7.477 7.496 1.310 0.000 SI - 42
149.479 137.405 127.015 128.528 128.860 76.684 77.001 77.319 83.303 24.770 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm SI - 43
10 9 8 7 6 5 4 3 2 1 0 ppm 0.484 0.618 4.000 2.346 13.737 7.267 5.666 5.846 5.859 5.866 1.261 1.775 1.794 1.812 1.830 1.849 2.270 2.290 2.309 2.328-0.000 SI - 44
SI - 45
5.691 2.354 2.336 2.317 2.298 10 9 8 7 6 5 4 3 2 1 0 ppm SI - 46
5.692 2.331 2.314 2.297 11 10 9 8 7 6 5 4 3 2 1 0 ppm SI - 47
5.888 5.875 10 9 8 7 6 5 4 3 2 1 0 ppm SI - 48
10 9 8 7 6 5 4 3 2 1 0 ppm 1.053 0.987 0.659 5.689 5.849 5.854 6.160-0.049 SI - 49