Polyborylated Cyclohexadienes
FULL PAPER
1.28–1.35 (m, 2.6H; H6exo 30 and H5exo 31), 1.58 (dd, J=15.0, 2.5 Hz,
1H; H6endo 30), 1.84 (dd, J=ꢀ14.9, 1.8 Hz, 1.6H; H5endo 31), 3.04 (dd,
J=6.7, 2.4 Hz, 1H; H5exo 30), 3.45 (dd, J=6.3, 1.8 Hz, 1.6H; H6exo 31),
4.82 (s, 7.9H; Cp, 31), 4.93 (s, 5H; Cp, 30), 7.11–7.26 (m, 20.8H; 30 and
31), 7.54 (d, J=7.5 Hz, 2H; 30), 7.60 ppm (d, J=7.1 Hz, 2H; 31);
13C NMR (CDCl3): d=ꢀ0.1 (CH3, TMS, 30), 0.9 (CH3, TMS, 31), 24.3
(CH3, pin, 30), 24.5 (CH3, pin, 31), 24.6 (CH3, pin, 31), 24.7 (CH3, pin,
31), 25.1 (CH3, pin, 31), 25.1 (CH3, pin, 30), 25.3 (CH3, pin, 30), 25.4
(CH3, pin, 30), 38.7 (CH2, C6, 30), 41.4 (CH2, C5, 31), 70.4 (CH, C6, 31),
72.8 (CH, C5, 30), 65.5 (C, C1, 30 and 31), 82.1 (C, pin, 31), 82.2 (C, pin,
30), 82.9 (CH, Cp, 30), 83.2 (CH, Cp, 31), 83.8 (C, pin, 30 and 31), 106.1
(C, C3, 30), 106.4 (C, C3, 31), 124.2 (CHarom, 31), 125.2 (CHarom, 30), 126.2
(CHarom, 30), 126.4 (CHarom, 31), 126.5 (CHarom, 30), 126.7 (CHarom, 31),
126.8 (CHarom, 30), 127.2 (CHarom, 31), 127.5 (2C, CHarom, 31), 131.4
(CHarom, 30), 131.6 (CHarom, 30), 141.2 (C, 31), 142.3 (C, 30), 146.7 (C,
30), 149.2 ppm (C, 31); C2 and C4 unobserved; IR (neat): n˜ =693, 759,
803, 835, 1070, 1140, 1250, 1292, 2974 cmꢀ1; HRMS (ES+): m/z calcd for
C38H51B2CoO5SiNa: 719.2922; found: 719.2913.
Data for 35: Red oil; 1H NMR (CDCl3): d=1.00 (s, 6H; pin), 1.06 (s,
6H; pin), 1.20 (s, 6H; pin), 1.24–1.30 (m, 9H; pin and Et-CH3), 1.72 (dd,
J=ꢀ15.4, 2.3 Hz, 1H; H6exo), 2.95 (dd, J=ꢀ15.2, 11.6 Hz, 1H; H6endo),
3.39 (dd, J=11.6, 2.0 Hz, 1H; H5endo), 3.72–3.80 (m, 1H), 3.93–4.01 (m,
1H), 4.88 (s, 5H; Cp), 7.00–7.26 ppm (m, 10H); 13C NMR (CDCl3): d=
15.7 (CH3), 24.6 (CH3, pin), 24.9 (CH3, pin), 25.0 (2C, CH3, pin), 40.8
(CH2, C6), 41.4 (CH, C5), 62.8 (CH2), 81.8 (CH, Cp), 82.0 (C, pin), 83.7
(C, pin), 97.8 (C), 108.9 (C), 124.9 (CHarom), 125.7 (CHarom), 126.3
(CHarom), 127.3 (CHarom), 127.8 (CHarom), 131.2 (CHarom), 141.9 (C),
147.7 ppm (C); C1 and C4 unobserved; IR (neat): n˜ =700, 1143, 1261,
1311, 1379, 2977 cmꢀ1; elemental analysis calcd (%) for C37H47B2CoO5: C
68.13, H 7.26; found: C 68.12, H 7.59
Data for 38: Red oil; 1H NMR (CDCl3): d=0.94–0.99 (m, 9H; pin and
Bu-CH3), 1.05 (s, 6H; pin), 1.17 (s, 6H; pin), 1.27 (s, 6H; pin), 1.45–1.54
(m, 2H), 1.56–1.65 (m, 2H), 1.69 (dd, J=ꢀ15.4, 2.3 Hz, 1H; H6exo), 2.95
(dd, J=ꢀ15.2, 11.6 Hz, 1H; H6endo), 3.38 (dd, J=11.6, 2.2 Hz, 1H;
H5endo), 3.61–3.68 (m, 1H), 3.86–3.93 (m, 1H), 4.87 (s, 5H; Cp), 7.00–
7.17 (m, 9H), 7.22–7.27 ppm (m, 1H); 13C NMR (CDCl3): d=15.1 (CH3),
19.6 (CH2), 24.8 (CH3, pin), 24.9 (CH3, pin), 25.0 (2C, CH3, pin), 32.4
(CH2), 40.9 (CH2, C6), 41.4 (CH, C5), 66.9 (CH2), 81.7 (CH, Cp), 82.0 (C,
pin), 83.6 (C, pin), 97.6 (C), 108.9 (C), 124.9 (CHarom), 125.7 (CHarom),
126.3 (CHarom), 127.3 (CHarom), 127.8 (CHarom), 131.2 (CHarom), 142.0 (C),
147.8 ppm (C); C1 and C4 unobserved; IR (neat): n˜ =700, 1141, 1260,
1309, 1371, 2929 cmꢀ1; HRMS (ES+): m/z calcd for C39H51B2CoO5Na:
703.3152; found: 703.3177; elemental analysis calcd (%) for
C39H51B2CoO5: C 68.85, H 7.56; found: C 69.23, H 7.64.
Data for 39: Red solid; m.p. 2208C; 1H NMR (CDCl3): d=0.72 (dd, J=
9.5, 4.4 Hz, 1H; H5exo), 0.89 (s, 6H; pin), 0.90 (s, 6H; pin), 0.98 (s, 6H;
pin), 1.04 (s, 6H; pin), 1.16 (dd, J=ꢀ14.6, 9.6 Hz, 1H; H6exo), 1.36 (s,
6H; pin), 1.37 (s, 6H; pin), 1.81 (dd, J=ꢀ14.8, 4.6 Hz, 1H; H6endo), 4.77
(s, 5H; Cp), 7.07–7.23 (m, 8H), 7.62 ppm (d, J=7.6 Hz, 2H); 13C NMR
(CDCl3): d=24.4 (CH3, pin), 24.5 (CH3, pin), 24.6 (CH3, pin), 25.1 (CH3,
pin), 25.2 (CH3, pin), 25.6 (CH3, pin), 31.6 (CH2, C6), 67.3 (C, C1), 82.3
(C, pin), 82.5 (C, pin), 83.4 (CH, Cp), 83.7 (C, pin), 106.7 (C, C3), 124.1
(CHarom), 126.1 (CHarom), 127.4 (2C, CHarom), 127.5 (2C, CHarom), 142.0
(C), 149.9 ppm (C); C2, C4 and C5 unobserved; IR (neat): n˜ =699, 1141,
1310, 1370, 2976 cmꢀ1; HRMS (ES+): m/z calcd for C41H54B3CoO6Na:
757.3429; found: 757.3445.
Data for 45: Red solid; m.p. 1808C; 1H NMR (CDCl3): d=ꢀ0.10 (d, J=
8.1 Hz, 1H; H5exo), 0.13 (s, 9H; TMS), 0.78 (s, 6H; pin), 0.99 (s, 6H;
pin), 1.03 (s, 6H; pin), 1.12 (s, 6H; pin), 1.25 (s, 6H; pin), 1.28 (s, 6H;
pin), 1.78 (d, J=8.1 Hz, 1H; H6exo), 4.95 (s, 5H; Cp), 7.08–7.26 (m, 8H),
7.62 ppm (d, J=7.3 Hz, 2H); 13C NMR (CDCl3): d=0.00 (CH3, TMS),
22.0 (CH3, pin), 22.8 (CH, C5), 23.0 (CH3, pin), 23.2 (CH3, pin), 24.0 (2C,
CH3, pin), 24.6 (CH3, pin), 70.2 (C, C1), 79.9 (C, pin), 80.7 (C, pin), 81.7
(C, pin), 82.1 (CH, Cp), 101.0 (C, C3), 123.2 (CHarom), 124.1 (CHarom),
124.8 (CHarom), 125.0 (CHarom), 128.2 (CHarom), 129.8 (CHarom), 141.1 (C),
147.1 ppm (C); C2, C4 and C6 unobserved; IR (neat): n˜ =699, 838, 1139,
1243, 1307, 1371, 2977 cmꢀ1
;
HRMS (ES+): m/z calcd for
C44H62B3CoO6SiNa: 829.3825; found: 829.3839.
Data for syn-46: Red solid; m.p. 2018C; 1H NMR (CDCl3): d=0.72–1.40
(m, 6H), 0.76 (s, 6H; pin), 0.85 (d, J=ꢀ8.6 Hz, 1H; H8exo), 0.88 (s, 6H;
pin), 1.11 (s, 12H; pin), 1.89 (bs, 1H; H7 or H9), 2.48 (bs, 1H; H7 or H9),
3.71 (d, J=ꢀ8.6 Hz, 1H; H8endo), 4.94 (s, 5H; Cp), 7.13–7.25 (m, 6H),
7.45 (d, J=7.6 Hz, 2H), 7.67–7.68 ppm (m, 2H); 13C NMR (CDCl3): d=
24.4 (CH3, pin), 25.1 (CH3, pin), 25.2 (CH3, pin), 25.3 (CH3, pin), 30.3
(CH2), 30.4 (CH2), 32.6 (CH2), 39.3 (CH), 41.6 (CH), 48.4 (CH), 54.0
(CH), 82.2 (C, pin), 83.7 (C, pin), 84.1 (CH, Cp), 103.8 (C3), 125.2
(CHarom), 126.3 (CHarom), 127.0 (CHarom), 127.1 (CHarom), 130.8 (CHarom),
131.2 (CHarom), 142.8 (C), 148.5 ppm (C); C1, C2 and C4 unobserved; IR
(neat): n˜ =696, 787, 1141, 1368, 2341, 2360, 2862, 2974 cmꢀ1; elemental
analysis calcd (%) for C40H49B2CoO4: C 71.24, H 7.32; found: C 71.06, H
7.34.
Data for anti-46: Red solid; m.p. 2308C; 1H NMR (CDCl3): d=0.47 (d,
J=ꢀ10.0 Hz, 1H; H8), 0.86–1.34 (m, 5H), 0.88 (s, 6H; pin), 0.95 (s, 6H;
pin), 1.07 (s, 12H; pin), 1.78 (d, J=3.5 Hz, 1H; H7 or H9), 1.88 (d, J=
3.5 Hz, 1H; H7 or H9), 2.11 (d, J=9.4 Hz, 1H; H5 or H6), 2.22 (d, J=
9.4 Hz, 1H; H5 or H6), 4.62 (s, 5H; Cp), 7.02–7.37 (m, 8H), 7.61 ppm (d,
J=7.3 Hz, 2H); 13C NMR (CDCl3): d=24.8 (CH3, pin), 24.9 (CH3, pin),
25.1 (CH3, pin), 25.4 (CH3, pin), 29.0 (CH2), 29.5 (CH2), 31.6 (CH2), 40.5
(CH), 43.3 (CH), 50.6 (CH), 53.0 (CH), 71.5 (C1) 81.9 (C, pin), 82.6 (CH,
Cp), 83.6 (C, pin), 106.7 (C3), 124.2 (CHarom), 126.1 (CHarom), 126.5
(CHarom), 127.4 (CHarom), 128.4 (2C, CHarom), 142.4 (C), 149.1 ppm (C); C2
and C4 unobserved; IR (neat): n˜ =697, 802, 1141, 2866, 2922 cmꢀ1; ele-
mental analysis calcd (%) for C40H49B2CoO4: C, 71.24; H, 7.32; found: C,
71.11; H, 7.15.
1
Data for 47: White solid; m.p. 2128C; H NMR (CDCl3): d=0.55 (s, 6H;
pin), 0.71 (s, 6H; pin), 0.98 (s, 6H; pin), 1.12 (s, 6H; pin), 1.28–1.31 (m,
2H), 1.52–1.58 (m, 3H), 1.93–2.15 (m, 3H), 2.74–2.91 (m, 2H), 7.17–
7.33 ppm (m, 10H); 13C NMR (CDCl3): d=24.0 (CH3, pin), 24.4 (2C,
CH3, pin), 24.9 (CH3, pin), 30.1 (CH2), 31.0 (CH2), 34.7 (CH2), 43.0 (CH),
46.1 (CH), 47.1 (CH), 47.3 (CH), 82.8 (C, pin), 83.0 (C, pin), 126.4
(CHarom), 126.9 (CHarom), 127.5 (CHarom), 128.0 (2C, CHarom), 128.6
(CHarom), 144.0 (C), 144.3 (C), 144.7 (C), 147.6 ppm (C); C2 and C4 unob-
served; IR (neat): n˜ =697, 802, 1141, 2866, 2922 cmꢀ1; HRMS (ES+):
m/z calcd for C35H44B2O4Na: 573.3323; found: 573.3358.
Data for anti-48: Red solid; m.p. 2058C; 1H NMR (CDCl3): d=0.86 (s,
6H; pin), 1.00 (s, 6H; pin), 1.08 (s, 6H; pin), 1.12 (s, 6H; pin), 2.51 (dd,
J=16.7, 4.3 Hz, 1H), 3.08, (dd, J=16.7, 9.4 Hz, 1H), 3.36 (dt, J=9.8,
4.3 Hz, 1H; H5endo), 4.16 (d, J=10.1 Hz, 1H; H6endo), 4.72 (s, 5H; Cp),
6.23 (d, J=7.6 Hz, 1H), 6.75 (t, J=7.6 Hz, 1H), 6.90–7.00 (m, 2H), 7.15–
7.30 (m, 8H), 7.72 ppm (d, J=7.3 Hz, 2H); 13C NMR (CDCl3): d=24.7
(CH3, pin), 25.0 (CH3, pin), 25.1 (CH3, pin), 25.2 (CH3, pin), 40.5 (CH2),
46.3 (CH, C5), 54.6 (CH, C6), 72.5 (C, C1), 82.1 (C, pin), 83.2 (CH, Cp),
83.6 (C, pin), 107.2 (C, C3), 124.2 (CHarom), 124.6 (CHarom), 124.8
(CHarom), 125.2 (CHarom), 125.9 (CHarom), 126.1 (CHarom), 126.4 (CHarom),
127.5 (CHarom), 129.1 (CHarom), 131.7 (CHarom), 141.9 (C), 142.4 (C), 145.2
(C), 148.7 ppm (C); C2 and C4 unobserved; IR (neat): n˜ =696, 744, 1140,
1263, 1389, 2978 cmꢀ1; HRMS (ES+): m/z calcd for C42H47B2CoO4Na:
719.2890; found: 719.2853.
Data for 40: Red solid; m.p. 2298C; 1H NMR (CDCl3): d=0.81–0.86 (m,
7H; pin and H6exo), 0.97 (s, 6H; pin), 1.00 (s, 6H; pin), 1.14 (s, 6H; pin),
1.18 (s, 6H; pin), 1.19 (s, 6H; pin), 1.38 (dd, J=8.9, 4.3 Hz, 1H; H5exo),
1.71 (dd, J=ꢀ14.1, 3.8 Hz, 1H; H5endo), 4.92 (s, 5H; Cp), 7.05–7.24 (m,
8H), 7.56 ppm (d, J=7.1 Hz, 2H); 13C NMR (CDCl3): d=24.2 (CH3,
pin), 24.6 (CH3, pin), 24.8 (CH3, pin), 24.9 (CH3, pin), 25.0 (CH3, pin),
25.5 (CH3, pin), 29.1 (CH2, C5), 71.8 (C, C1), 82.1 (C, pin), 82.3 (C, pin),
83.2 (CH, Cp), 83.6 (C, pin), 105.4 (C, C3), 124.6 (CHarom), 126.0
(CHarom), 126.6 (CHarom), 127.0 (CHarom), 129.2 (CHarom), 131.7 (CHarom),
142.6 (C), 149.6 ppm (C); C2, C4 and C6 unobserved; IR (neat): n˜ =700,
805, 1142, 1262, 1309, 1371, 2928, 2977 cmꢀ1; HRMS (ES+): m/z calcd
for C41H54B3CoO6Na: 757.3429; found: 757.3464.
Data for syn-48: Red solid; m.p. 2178C; 1H NMR (CDCl3): d=0.83 (s,
6H; pin), 0.98 (s, 6H; pin), 1.16 (s, 6H; pin), 1.22 (s, 6H; pin), 2.16–2.26
(m, 2H), 3.38–3.49 (m, 2H), 4.85 (s, 5H; Cp), 5.52 (d, J=7.6 Hz, 1H),
6.69 (t, J=7.6 Hz, 1H), 7.05 (t, J=7.4 Hz, 1H), 7.12–7.30 (m, 9H), 7.71–
7.78 ppm (m, 2H); 13C NMR (CDCl3): d=24.2 (CH3, pin), 25.2 (CH3,
pin), 25.3 (2C, CH3, pin), 42.7 (CH2), 44.1 (CH, C5), 53.0 (CH, C6), 77.3
Chem. Eur. J. 2007, 13, 5408 – 5425
ꢀ 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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