Supplementary data Nickel-catalysed addition of organoboronates to 1,3-dienes

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Supplementary data

Nickel-catalysed addition of organoboronates to 1,3-dienes
Eiji Shirakawa,* Go Takahashi, Teruhisa Tsuchimoto and Yusuke Kawakami
Graduate School of Materials Science, Japan Advanced Institute of Science and Technology, Asahidai, Tatsunokuchi, Ishikawa 923-1292, Japan. Fax: 81 761 51 1631; Tel: 81 761 51 1631; E-mail: shira@jaist.ac.jp
¹H NMR and GC–MS data of hydroarylation and -alkenylation products

2,3-Dimethyl-3-(p-tolyl)-1-butene (3a). ¹H NMR (300 MHz, CDCl₃)  = 1.42 (s, 6 H), 1.54 (s, 3 H), 2.33 (s, 3 H), 4.73 (m, 1 H), 4.92 (m, 1 H), 7.05–7.13 (m, 2 H), 7.14–7.23 (m, 2 H); GC–MS m/z (relative intensity) 174 (M⁺, 28), 159 (100), 144 (13), 133 (31), 117 (14), 105 (33), 91 (21), 77 (14), 65 (7), 51 (5).

2,3-Dimethyl-1-(p-tolyl)-2-butene (4a). ¹H NMR (300 MHz, CDCl₃)  = 1.60 (s, 3 H), 1.74 (s, 3 H), 1.80 (s, 3 H), 2.33 (s, 3 H), 3.37 (s, 2 H), 7.00–7.11 (m, 4 H); GC–MS m/z (relative intensity) 174 (M⁺, 41), 159 (100), 144 (14), 131 (20), 117 (12), 105 (24), 91 (17), 77 (18), 67 (14), 51 (7).

2,3-Dimethyl-4-(p-tolyl)-1-butene (4’a). ¹H NMR (300 MHz, CDCl₃)  = 0.98 (d, J = 6.6 Hz, 3 H), 1.73 (s, 3 H), 2.32 (s, 3 H), 2.36–2.54 (m, 2 H), 2.70–2.81 (m, 1 H), 4.64–4.71 (m, 2 H), 7.00–7.12 (m, 4 H); GC–MS m/z (relative intensity) 174 (M⁺, 14), 159 (3), 141 (1), 128 (1), 115 (2), 105 (100), 91 (3), 77 (6), 69 (2), 51 (2).

2,3-Dimethyl-3-(4-methoxyphenyl)-1-butene (3b). ¹H NMR (300 MHz, CDCl₃)  = 1.40 (s, 6 H), 1.52 (m, 3 H), 3.79 (s, 3 H), 4.84–4.87 (m, 1 H), 4.94–4.97 (m, 1 H), 6.79–6.86 (m, 2 H), 7.18–7.24 (m, 2 H); GC–MS m/z (relative intensity) 190 (M⁺, 33), 175 (68), 160 (18), 149 (100), 128 (8), 121 (29), 109 (10), 91 (34), 77 (24), 65 (12), 51 (8).

2,3-Dimethyl-1-(4-methoxyphenyl)-2-butene (4b). ¹H NMR (300 MHz, CDCl₃)  = 1.58 (s, 3 H), 1.72 (s, 3 H), 1.78 (s, 3 H), 3.33 (s, 2 H), 3.78 (s, 3 H), 6.79–6.85 (m, 2 H), 7.03–7.10 (m, 2 H); GC–MS m/z (relative intensity) 190 (M⁺, 52), 175 (100), 160 (27), 147 (27), 128 (8), 121 (45), 108 (28), 91 (32), 77 (33), 67 (13), 51 (15).

2,3-Dimethyl-3-(4-trifluoromethylphenyl)-1-butene (3c). ¹H NMR (300 MHz, CDCl₃)  = 1.44 (s, 6 H), 1.50–1.52 (m, 3 H), 4.91–4.95 (m, 1 H), 5.00–5.02(m, 1 H), 7.38–7.44 (m, 2 H), 7.50–7.56 (m, 2 H); GC–MS m/z (relative intensity) 228 (M⁺, 6), 213 (41), 185 (11), 173 (5), 159 (100), 151 (8), 129 (9), 117(9), 109 (5), 91 (3), 77 (7), 57 (4), 51 (5).

2,3-Dimethyl-1-(4-trifluoromethylphenyl)-2-butene (4c). ¹H NMR (300 MHz, CDCl₃)  = 1.57–1.61 (m, 3H), 1.71–1.76 (m, 3 H), 1.76–1.80 (m, 3 H), 3.44 (s, 2 H), 7.21–7.28 (m, 2 H), 7.48–7.54 (m, 2 H); GC–MS m/z (relative intensity) 228 (M⁺, 59), 213 (100), 209 (10), 185 (39), 173 (7), 159 (44), 144 (6), 129 (10), 115 (10), 109 (13), 91 (7), 83 (6), 69 (25), 53 (12).

2,3-Dimethyl-3-(3-aminophenyl)-1-butene (3d). ¹H NMR (300 MHz, CDCl₃)  = 1.38 (s, 6 H), 1.52–1.54 (m, 3 H), 4.84–4.87 (m, 1 H), 4.97–4.50 (m, 1 H), 6.48–6.54 (m, 1 H), 6.62–6.65 (m, 1 H), 6.69–6.74 (m, 1 H), 7.04–7.01 (m, 1 H); GC–MS m/z (relative intensity) 175 (M⁺ 23), 160 (100), 145 (23), 130 (9), 118 (6), 106 (13), 93 (14), 77 (9), 65 (9), 51 (3).

2,3-Dimethyl-1-(3-aminophenyl)-2-butene (4d). ¹H NMR (300 MHz, CDCl₃)  = 1.57–1.61 (m, 3 H), 1.71–1.74 (m, 3 H), 1.76–1.79 (m, 3 H), 3.30 (s, 2 H), 6.45–6.54 (m, 2 H), 6.54–6.59 (m, 1 H), 7.02–7.09 (m, 1 H); GC–MS m/z (relative intensity) 175 (M⁺, 100), 160 (89), 145 (35), 132 (26), 118 (7), 106 (58), 93 (36), 77 (24), 65 (19), 51 (8).

2,3-Dimethyl-3-(2-naphthyl)-1-butene (3e). ¹H NMR (300 MHz, CDCl₃)  = 1.52 (s, 6 H), 1.52–1.54 (m, 3 H), 4.92–4.96 (m, 1 H), 5.04–5.06 (m, 1 H), 7.38–7.49 (m, 3 H), 7.72–7.84 (m, 4 H); GC–MS m/z (relative intensity) 210 (M⁺, 54), 195 (100), 180 (22), 165 (55), 141 (47), 128 (25), 115 (16), 102 (5), 89 (23), 76 (15), 63 89), 51 (9).

2,3-Dimethyl-1-(2-naphthyl)-2-butene (4e). ¹H NMR (300 MHz, CDCl₃)  = 1.60–1.65 (m, 3 H), 1.74–1.79 (m, 3 H), 1.82–1.86 (m, 3 H), 3.55 (s, 2 H), 7.26–7.32 (m, 1 H), 7.35–7.49 (m, 2 H), 7.54–7.58 (m, 1 H), 7.66-7.85 (m, 3 H); GC–MS m/z (relative intensity) 210 (M⁺, 76), 195 (100), 180 (24), 165 (53), 141 (45), 128 (45), 115 (42), 102 (3), 89 (16), 82 (30), 67 (13), 51 (7).

2,3-Dimethyl-3-(3-thienyl)-1-butene (3f). ¹H NMR (300 MHz, CDCl₃)  = 1.43 (s, 6 H), 1.55–1.59 (s, 3 H), 4.79–4.83 (m, 1 H), 4.87–4.90 (m, 1 H), 6.92 (dd, J = 4.8, 1.5 Hz, 1 H), 6.97 (dd, J = 3.0, 1.5 Hz, 1 H), 7.20–7.24 (m, 1 H); GC–MS m/z (relative intensity) 166 (M⁺, 45), 151 (100), 135 (5), 125 (32), 105 (6), 97 (49), 77 (5), 65 (6), 51 (5).

2,3-Dimethyl-1-(3-thienyl)-2-butene (4f). ¹H NMR (300 MHz, CDCl₃)  = 1.62–1.65 (m, 3 H), 1.69–1.73 (m, 3 H), 1.75–1.78 (s, 3 H), 3.36 (s, 3 H), 6.86–6.90 (m, 2 H), 7.20–7.24 (m, 1 H); GC–MS m/z (relative intensity) 166 (M⁺, 95), 151 (100), 136 (5), 117 (13), 105 (13), 97 (77), 82 (11), 67 (24), 53 (17).

(E)-2,3,3-Trimethyl-1,4-undecadiene (3g). ¹H NMR (300 MHz, CDCl₃)  = 0.84–0.92 (m, 3 H), 1.12 (s, 6 H), 1.21–1.40 (m, 8 H), 1.67–1.70 (m, 3 H), 1.93–2.03 (m, 2 H), 4.70–4.73 (m, 1 H), 4.75–4.78 (m, 1 H), 5.28–5.43 (m, 2 H); GC–MS m/z (relative intensity) 194 (M⁺, 3), 179 (7), 151 (5), 137 (3), 123 (15), 109 (100, 95 (84), 81 (85), 67 (80), 55 (52).

(E)-2,3-Dimethyl-2,5-dodecadiene (4g). ¹H NMR (300 MHz, CDCl₃)  = 0.84–0.92 (m, 3 H), 1.21–1.40 (m, 8 H), 1.58–1.63 (m, 3 H), 1.64–1.68 (m, 6 H), 1.93–2.04 (m, 2 H), 2.69 (d, J = 5.7 Hz, 2 H), 5.25–5.45 (m, 2 H); GC–MS m/z (relative intensity) 194 (M⁺, 12), 151 (3), 137 (1), 123 (11), 109 (30), 95 (68), 81 (100), 67 (59), 55 (39).

(E)-1-Phenyl-3,3,4-trimethyl-1,4-pentadiene (3h). ¹H NMR (300 MHz, CDCl₃)  = 1.26 (s, 6 H), 1.73–1.77 (m, 3 H), 4.79–4.83 (m, 1 H), 4.85–4.87 (m, 1 H), 6.20 (d, J = 16.2 Hz, 1 H), 6.35 (d, J = 16.2 Hz, 1 H), 7.15–7.40 (m, 5 H); GC–MS m/z (relative intensity) 186 (M⁺, 28), 171 (100), 156 (28), 143 (100), 129 (41), 115 (25), 105 (11), 91 (85), 77 (26), 65 (10), 51 (13).

(E)-4,5-Dimethyl-1-phenyl-1,4-hexadiene (4h). ¹H NMR (300 MHz, CDCl₃)  = 1.62–1.76 (m, 9 H), 2.92 (d, J = 6.6 Hz, 2 H), 6.16 (dt, J = 15.6, 6.6 Hz, 1 H), 6.30–6.40 (m, 1 H), 7.16–7.40 (m, 5 H); GC–MS m/z (relative intensity) 186 (M⁺, 59), 171 (73), 156 (16), 143 (90), 129 (41), 115 (38), 104 (20), 91 (100), 77 (24), 67 (30), 55 (32).

(Z)-2,3-Diphenyl-1-(p-tolyl)-2-butene ((Z)-6a). ¹H NMR (300 MHz, CDCl₃)  = 1.91 (s, 3 H), 2.24 (s, 3 H), 3.58 (s, 2 H), 6.75–7.00 (m, 4 H), 7.06–7.44 (m, 10 H); GC–MS m/z (relative intensity) 298 (M⁺, 72), 283 (48), 220 (22), 205 (63), 191 (52), 178 (50), 165 (27), 152 (14), 128 (17), 115 (77), 105 (39), 91 (100), 77 (54), 65 (21), 51 (23).

(E)-2,3-Diphenyl-1-(p-tolyl)-2-butene ((E)-6a). ¹H NMR (300 MHz, CDCl₃)  = 2.23 (s, 3 H), 2.30 (s, 3 H), 3.91 (s, 2 H), 6.87–7.17 (m, 14 H).

(E)-3-Methyl-1,3,4-triphenyl-1,4-pentadiene (5b).¹H NMR (300 MHz, CDCl₃)  = 1.60 (s, 3 H), 5.33 (d, J = 1.2 Hz, 1 H), 5.37 (d, J = 1.2 Hz, 1 H), 6.16 (d, J = 16.2 Hz, 1 H), 6.64 (d, J = 16.2 Hz, 1 H), 6.89–7.00 (m, 2 H), 7.08–7.52 (m, 13 H).

(1E,4Z)-1,4,5-Triphenyl-1,4-hexadiene ((Z)-6b).¹H NMR (300 MHz, CDCl₃)  = 1.89 (s, 3 H), 3.13 (d, J = 6.3 Hz, 2 H), 6.02 (dt, J = 16.2, 6.3 Hz, 1 H), 6.14 (d, J = 16.2 Hz, 1 H), 7.13–7.42 (m, 15 H); GC–MS m/z (relative intensity) 310 (M⁺, 14), 295 (5), 232 (4), 219 (69), 204 (30), 191 (16), 178 (23), 165 (12), 152 (6), 128 (5), 115 (31), 105 (8), 91 (100), 77 (14), 65 (7), 51 (7).

(1E,4E)-1,4,5-Triphenyl-1,4-hexadiene ((E)-6b). This compound, produced only in a small amount, was not isolated and could not be characterized by ¹H NMR. Because the GC–MS analysis implies that the compound is an isomer of 5b and (Z)-6b, we characterized this as (E)-6b. GC–MS m/z (relative intensity) 310 (M⁺, 13), 296 (2), 281 (3), 253 (3), 233 (2), 219 (73), 204 (30), 191 (14), 178 (18), 165 (12), 152 (8), 128 (5), 115 (36), 105 (6), 91 (100), 77 (20), 65 (9), 51 (9).