K.S. Dunne et al. / Journal of Organometallic Chemistry 691 (2006) 5246–5259
5255
product as a cloudy oil (E:Z = 5:1). Yield: 80 mg (85%); Rf
0.3 (cyclohexane/EtOAc 4:1); 1H NMR (400 MHz,
CDCl3): d 7.63–7.70 (m, 4H; Ph–H), 7.51–7.55 (m, 2H;
Ph–H), 7.43–7.47 (m, 4H; Ph–H), 5.36 (m, 2H; PCH2CH),
4.17. Diphenyl(4-trimethylsilylbut-2-enyl)phosphine borane
15b
Procedure
A from allyldiphenylphosphine borane
3
3.58 (d, J(H,P) 11.9 Hz, 6H; OCH3), 2.71 (m, 4H; PCH2),
(100 mg, 0.44 mmol) and allyltrimethylsilane (0.21 ml,
1.32 mmol) in dichloromethane (1.5 ml) using 0.04 equiv.
Grubbs’ 2nd generation catalyst (15 mg, 0.018 mmol) over
24 h. The residue was purified by flash chromatography
(cyclohexane/EtOAc 19:1) to afford the product as a white
solid (E:Z = 5:1). Yield: 122 mg (85%); Rf 0.3 (cyclohexane/
EtOAc 19:1); m.p. 46–50 °C; 1H NMR (400 MHz, CDCl3):
d 7.65–7.70 (m, 4H; Ph–H)E+Z, 7.40–7.49 (m, 6H; Ph–
H)E+Z, 5.60 (m, 1H; PCH2CHCH)Z, 5.48 (m, 1H;
PCH2CHCH)E, 5.31 (m, 1H; PCH2CHCH)Z, 5.23 (m, 1H;
1
0.72 ppm (brq, 6H, J(H,B) 80 Hz, BH3); 13C NMR
4
(101 MHz, CDCl3) d 132.0 (d, J(C,P) 1.8 Hz, Ph–Cpara),
2
1
130.9 (d, J(C,P) 10.7 Hz, Ph–Cortho), 130.1 (d, J(C,P)
3
54.6 Hz, Ph–Cipso), 128.5 (d, J(C,P) 10.0 Hz, Ph–Cmeta),
3
2
124.5 (dd, J(C,P) 6.1, J(C,P) 11.1 Hz, PCH2CH), 53.95 (d,
2J(C,P) 1.9 Hz, OCH3), 35.1 (d, J(C,P) 40.7 Hz, PCH2)E;
1
31P NMR (162 MHz, CDCl3): d 113.6 ppm (q, J(P,B)
1
75 Hz); IR (film): m 2385 (B–H), 1438 cmÀ1 (P–Ph); HRMS
(FI): m/z calcd for C18H25BO2P2 [MÀBH3]+Æ: 346.1423;
1
3
2
found: 346.1362. Signals overlapping on the H NMR for
PCH2CHCH)E, 3.03 (dd, J(H,H) 7.7, J(H,P) 12.4 Hz, 2H;
1
3
2
dl and meso isomers except for the OMe group: H NMR
(400 MHz, CDCl3): d 3.58 (d, J(H,P) 11.9 Hz, OCH3) for
dl or meso, 3.56 (d, J(H,P) 11.8 Hz, OCH3) for dl or
PCH2)E/Z, 3.01 (dd, J(H,H) 7.8, J(H,P) 12.0 Hz, 2H;
3
3
4
PCH2)E/Z, 1.39 (dd, J(H,H) 7.9, J(H,H) 3.5 Hz, 2H; CH2Si-
3
1
Me3)E+Z, 1.01 (brq, J(H,B) 80 Hz, 3H; BH3)E+Z, À0.02 (s,
meso.
9H; Si(CH3)3)Z, À0.16 ppm (s, 9H; Si(CH3)3)E; 13C NMR
(101 MHz, CDCl3)
d
132.9 (d, 2J(C,P) 11.3 Hz,
2
4.16. Diphenyltridec-2-enylphosphine borane 15a
PCH2CHCH)E, 132.5 (d, J(C,P) 9.1 Hz, PCH2CHCH)Z,
132.3 (d, J(C,P) 8.7 Hz, Ph–Cmeta)E, 132.0 (d, J(C,P)
3
3
4
Procedure
A
from allyldiphenylphosphine borane
9.0 Hz, Ph–Cmeta)Z, 131.1 (d, J(C,P) 2.4 Hz, Ph–Cpara)Z,
4
1
(100 mg, 0.44 mmol) and 1-dodecene (0.28 ml, 1.26 mmol)
in dichloromethane (1.5 ml) using 0.04 equiv. Grubbs’
2nd generation catalyst (15 mg, 0.018 mmol) over 24 h.
The residue was purified by flash chromatography (hex-
ane/EtOAc 19:1) to afford the product as a colourless oil
(E:Z = 9:1). Yield: 100 mg (60%); Rf 0.5 (hexane/EtOAc
131.0 (d, J(C,P) 2.3 Hz, Ph–Cpara)E, 129.2 (d, J(C,P)
53.9 Hz, Ph–Cipso)E, 129.1 (d, J(C,P) 54.2 Hz, Ph–Cipso)Z,
1
2
3
128.6 (d, J(C,P) 9.8 Hz, Ph–Cortho
)
E+Z, 117.0 (d, J(C,P)
5.4 Hz, PCH2CH)E, 116.2 (d, J(C,P) 4.6 Hz, PCH2CH)Z,
3
30.7 (d, J(C,P) 36.2 Hz, PCH2)E, 25.1 (d, J(C,P) 36.7 Hz,
1
1
PCH2)Z, 23.2 (d, J(C,P) 1.9 Hz, CH2SiMe3)E, 18.8 (d,
4
1
19:1); H NMR (400 MHz, CDCl3): d 7.65–7.71 (m, 4H;
4J(C,P) 1.6 Hz, CH2SiMe3)Z, À1.8 (s, Si(CH3)3)Z,
À2.2 ppm (s, Si(CH3)3)E; 31P NMR (162 MHz, CDCl3): d
Ph–H)E+Z, 7.42–7.51 (m, 6H; Ph–H)E+Z, 5.54 (m, 2H;
PCH2CHCH)Z, 5.40 (m, 2H; PCH2CHCH)E, 3.05 (dd,
16.6 (q, J(P,B) 70 Hz)Z, 15.5 ppm (q, J(P,B) 70 Hz)E; IR
(film): m 2382 (B–H), 1437 cmÀ1 (P–Ph); HRMS (FI): m/z
calcd for C19H28BPSi M+Å: 326.1795; found: 326.1791.
1
1
2
3
3J(H,H) 7.9, J(H,P) 12.5 Hz, 2H; PCH2)Z; 3.00 (dd, J(H,H)
6.5, J(H,P) 12.2 Hz, 2H; PCH2)E, 1.92 (m, 2H;
2
PCH2(CH)2CH2)E, 1.85 (m, 2H; PCH2(CH)2CH2)Z, 1.33–
1.12 (m, 16H; (CH2)8)E+Z, ꢀ1.0 (brq, obscured, 3H;
4.18. 6-Bromohex-2-enyldiphenylphosphine borane 15c
BH3)E+Z, 0.90 ppm (t, J(H,H) 7.0 Hz, 3H; CH3)E+Z
;
13C
3
2
NMR (101 MHz, CDCl3) d 136.9 (d, J(C,P) 11.1 Hz,
Procedure A from allyldiphenyl-phosphine borane
PCH2CH)E, 135.1 (d, J(C,P) 11.1 Hz, PCH2CH)Z, 132.4
(100 mg, 0.44 mmol) and 5-bromopent-1-ene (0.16 ml,
1.32 mmol) in dichloromethane (1.5 ml) using 0.08 equiv.
Grubbs’ 2nd generation catalyst (30 mg, 0.036 mmol) over
48 h. The residue was purified by flash chromatography
(cyclohexane/EtOAc 9:1) to afford the E-isomer of the
product as a colourless oil. Yield: 65 mg (41%); Rf 0.3
2
(d, J(C,P) 9.0 Hz, Ph–Cmeta)E, 132.3 (d, J(C,P) 8.9 Hz, Ph–
3
3
4
C
meta)Z, 131.0 (d, J(C,P) 2.0 Hz, Ph–Cpara)Z, 131.0 (d,
4J(C,P) 2.0 Hz, Ph–Cpara)E, 129.9 (d, J(C,P) 52.9 Hz,
1
Ph–Cipso)Z, 129.1 (d, J(C,P) 54.2 Hz, Ph–Cipso)E, 128.6 (d,
1
2J(C,P) 9.9 Hz, Ph–Cortho)Z, 128.5 (d, 2J(C,P) 9.5, Ph–Cortho)E,
119.0 (d, J(C,P) 5.4 Hz, PCH2CHCH)E, 118.3 (d, J(C,P)
(cyclohexane/EtOAc 9:1); H NMR (400 MHz, CDCl3): d
3
3
1
5.0 Hz, PCH2CHCH)Z, 32.4 (d, 4J(C,P) 1.5 Hz,
7.62–7.67 (m, 4H; Ph–H), 7.41–7.49 (m, 6H; Ph–H), 5.39
PCH2(CH)2CH2)E, 31.8 (s, CH2)E, 30.5 (d, J(C,P)
(m, 2H; PCH2CHCH), 3.17 (t, 3J(H,H) 6.7 Hz, 2H; BrCH2),
1
35.8 Hz, PCH2)E, 29.53 (s, CH2)E, 29.50 (s, CH2)Z, 29.48
(s, CH2)E, 29.44 (s, CH2)Z, 29.38 (s, CH2)Z, 29.34 (s,
CH2)E, 29.30 (s, CH2)Z, 29.24 (s, CH2)E, 29.21 (s, CH2)Z,
29.04 (s, CH2)Z, 29.01 (s, CH2)E, 28.99 (s, CH2)E, 28.9 (s,
2.99 (dd, J(H,H) 7.0, J(H,P) 12.4 Hz, 2H; PCH2), 2.07 (m,
3
2
3
3
2H; BrCH2CH2CH2), 1.74 (tt, J(H,H) 6.9, J(H,H) 6.9 Hz,
1
2H; BrCH2CH2), 0.94 ppm (brq, J(H,B) 100 Hz, 3H;
BH3); 13C NMR (101 MHz, CDCl3) d 134.4 (d, J(C,P)
2
CH2)Z, 28.8 (s, CH2)E, 27.4 (d, J(C,P) 1.4 Hz,
11.1 Hz, PCH2CHCH), 132.3 (d, J(C,P) 8.9 Hz, Ph–Cmeta),
131.2 (d, J(C,P) 2.4 Hz, Ph–Cpara), 128.8 (d, J(C,P)
4
3
PCH2(CH)2CH2)Z, 25.6 (d, J(C,P) 35.5 Hz, PCH2)Z, 22.6
1
4
1
(s, CH2)E+Z, 14.0 ppm (s, CH3)E+Z
;
31P NMR (162 MHz,
54.3 Hz, Ph–Cipso), 128.7 (d, J(C,P) 9.8 Hz, Ph–Cortho),
2
CDCl3): d 16.0 ppm (q, J(P,B) 60 Hz)E+Z; IR (film): m
2384 (B–H), 1437 cmÀ1 (P–Ph); HRMS (FI): m/z calcd
for C25H38BP M+Å: 380.2804; found: 380.2804.
121.0 (d, J(C,P) 5.5 Hz, PCH2CH), 32.8 (s, BrCH2), 31.8
1
3
5
4
(d, J(C,P) 3.3 Hz, BrCH2CH2), 30.6 (d, J(C,P) 2.2 Hz,
BrCH2CH2CH2), 30.5 ppm (d, J(C,P) 35.6 Hz, PCH2); 31P
1