Takaki et al.
ylethylene (3a ) (85% yield) and oxidized with H2O2: white
solid; mp 156-157 °C; IR (Nujol) 1177 cm-1; 1H NMR (CDCl3)
δ 6.92-7.53 (16H, m), 7.58 (1H, d, J ) 21.0 Hz, olefinic), 7.64-
7.70 (4H, m); 13C NMR (CDCl3) δ 127.7 (d, J ) 1.5 Hz), 128.16,
128.22 (d, J ) 12.3 Hz), 128.7 (d, J ) 1.6 Hz), 128.9, 129.9 (d,
J ) 4.1 Hz), 130.2 (d, J ) 1.6 Hz), 131.0 (d, J ) 103.4 Hz),
131.8 (d, J ) 2.5 Hz), 132.3 (d, J ) 9.0 Hz), 134.9 (d, J ) 2.4
Hz), 135.2 (d, J ) 73.0 Hz), 135.7 (d, J ) 26.3 Hz), 143.0 (d, J
) 9.0 Hz); UV (EtOH) λmax 268 (ꢀ 1.24 × 104) nm [lit.16c λmax
(E)-isomer 268, (Z)-isomer 284]. Anal. Calcd for C26H21OP: C,
82.09; H, 5.56. Found: C, 82.07; H, 5.50.
(6H, m), 7.60-7.72 (4H, m); 13C NMR (CDCl3) δ 13.5, 13.6,
22.4 (d, J ) 1.6 Hz), 22.9 (d, J ) 3.3 Hz), 32.6 (d, J ) 7.4 Hz),
37.7 (d, J ) 13.1 Hz), 128.3 (d, J ) 12.3 Hz), 131.5, 131.6 (d,
J ) 11.8 Hz), 131.9 (d, J ) 96.8 Hz), 133.8 (d, J ) 100.0 Hz),
148.6(d, J ) 8.2 Hz); HRMS calcd for C20H25OP (M+) 312.1641,
found 312.1626.
(Z)-2-Dip h en ylp h osp h in yl-2-octen e (3f ′) [187471-88-1].
Isolated in 51% yield: colorless oil; IR (neat) 1188 cm-1; MS
1
m/z 312 (M+), 269 (M+ - Pr), 201 (Ph2PO+), 185 (Ph2P+); H
NMR (CDCl3) δ 0.79 (3H, t, J ) 6.9 Hz), 1.11-1.31 (6H, m),
1.74 (3H, d, J ) 12.3 Hz), 2.29-2.38 (2H, m), 6.41 (1H, dt, J
) 37.5, 6.3 Hz), 7.46-7.54 (6H, m), 7.66-7.72 (4H, m); 13C
NMR (CDCl3) δ 13.9, 22.3, 23.8 (d, J ) 14.0 Hz), 28.8, 30.4 (d,
J ) 6.6 Hz), 31.3, 126.9 (d, J ) 95.2 Hz), 128.4 (d, J ) 12.3
Hz), 131.48 (d, J ) 4.9 Hz), 131.54 (d, J ) 2.5 Hz), 133.4 (d, J
) 101.7 Hz), 149.8(d, J ) 8.2 Hz); HRMS calcd for C20H25OP
(M+) 312.1641, found 312.1624.
(E)-2-Diph en ylph osph in yl-2-tr im eth ylsilylstyr en e (3b′).
Isolated as (E)-2-diphenylphosphino-2-trimethylsilylstyrene
(3b) (69% yield) and oxidized with H2O2: white solid; mp 122-
1
123 °C; IR (Nujol) 1177 cm-1; H NMR (CDCl3) δ -0.03 (3H,
d, J ) 1.0 Hz), 0.0 (6H, s), 7.21-7.82 (16H, m); 13C NMR
(CDCl3) δ 1.1 (d, J ) 7.4 Hz), 1.5 (d, J ) 2.5 Hz), 127.2, 127.8,
127.9 (d, J ) 1.4 Hz), 128.0 (d, J ) 1.6 Hz), 128.4 (d, J ) 3.3
Hz), 128.5, 128.8, 131.4 (d, J ) 3.6 Hz), 131.9 (d, J ) 9.9 Hz),
133.4 (d, J ) 99.3 Hz), 134.6 (d, J ) 20.5 Hz), 139.0 (d, J )
41.1 Hz), 139.4 (d, J ) 77.9 Hz), 141.0 (d, J ) 6.6 Hz). Anal.
Calcd for C23H25OPSi: C, 73.37; H, 6.69. Found: C, 73.04; H,
6.57. Stereochemistry of 3b′ was confirmed by the selective
conversion to (E)-3d ′ with Bu4NF.
(Z)-1-Dip h en ylp h osp h in yl-3,3-d im eth yl-1-bu ten e (3g′).
Isolated in 52% yield: white solid; mp 116-117 °C; IR (Nujol)
1180 cm-1; MS m/z 284 (M+), 269 (M+-Me), 201 (Ph2PO+), 124
1
(PhPO+); H NMR (CDCl3) δ 1.21 (9H, s), 5.97 (1H, dd, J )
22.4, 14.6 Hz), 6.68 (1H, dd, J ) 43.5, 14.6 Hz), 7.41-7.50 (6H,
m), 7.71-7.77 (4H, m); 13C NMR (CDCl3) δ 30.3 (d J ) 9.8
Hz), 35.4 (d, J ) 5.7 Hz), 119.2 (d, J ) 97.5 Hz), 128.4 (d, J )
12.3 Hz), 130.8 (d, J ) 9.8 Hz), 131.3, 135.7 (d, J ) 105.0),
164.5. Anal. Calcd for C18H21OP: C, 76.04; H, 7.44. Found:
C, 76.14; H, 7.32.
1-P h en yl-2-diph en ylph osph in yl-1-pr open e (3c′) [62556-
17-6]. (E)-Isomer (major): isolated as (E)-1-phenyl-2-diphen-
ylphosphino-1-propene (3c) (67% yield) and oxidized with
H2O2: white solid; mp 129-130 °C; IR (Nujol) 1177 cm-1; MS
m/z 318 (M+), 303 (M+ - Me), 241 (M+ - Ph), 201 (Ph2PO+);
1H NMR (CDCl3) δ 2.03 (3H, d, J ) 14.0 Hz), 7.13 (1H, d, J )
22.2 Hz), 7.19-7.50 (11H, m), 7.66-7.71 (4H, m); 13C NMR-
(CDCl3) δ 15.0 (d, J ) 10.7 Hz), 128.3 (d, J ) 4.0 Hz), 128.5,
128.6, 129.4, 129.6 (d, J ) 40.6 Hz), 131.2 (d, J ) 102.5 Hz),
131.9 (d, J ) 2.5 Hz), 132.1 (d, J ) 9.8 Hz), 135.8 (d, J ) 18.9
Hz), 142.7 (d, J ) 11.5 Hz); HRMS calcd for C21H19OP (M+)
318.1175, found 318.1182. (Z)-Isomer (minor): isolated as (Z)-
1-phenyl-2-diphenylphosphino-1-propene (3c) (13% yield) and
oxidized with H2O2: white solid; mp 120-123 °C; IR (Nujol)
1173 cm-1; MS m/z 318 (M+), 303 (M+ - Me), 241 (M+ - Ph),
1-Dip h en ylp h osp h in yl-1-octen e (3h ′) [195148-53-9 a n d
178943-30-1]. (Z)-Isomer (major): isolated in 34% yield; white
1
solid; MS m/z 312 (M+), 255 (M+ - Bu), 241 (M+ - Pen); H
NMR (CDCl3) δ 0.83 (3H, t, J ) 7.1 Hz), 1.10-1.28 (6H, m),
1.34 (2H, quin, J ) 7.1 Hz), 2.54 (2H, qm, J ) 7.1 Hz), 6.11
(1H, ddt, J ) 25.6, 12.8, 3.0 Hz), 6.69 (1H, ddt, J ) 40.5, 12.8,
7.1 Hz), 7.42-7.51 (6H, m), 7.71-7.77 (4H, m); 13C NMR
(CDCl3) δ 14.0, 22.5, 28.76 (d, J ) 3.3 Hz), 28.78, 30.9 (d, J )
8.2 Hz), 31.5, 121.2 (d, J ) 100.9 Hz), 128.5 (d, J ) 12.2 Hz),
130.9 (d, J ) 9.8 Hz), 131.4 (d, J ) 2.5 Hz), 134.6 (d, J ) 103.4
Hz), 155.2. (E)-Isomer (minor): isolated in 4% yield; white
1
solid; H NMR (CDCl3) δ 0.87 (3H, t, J ) 7.0 Hz), 1.17-1.34
1
201 (Ph2PO+); H NMR (CDCl3) δ 1.90 (3H, dd, J ) 12.3, 1.5
(6H, m), 1.48 (2H, quin, J ) 7.0 Hz), 2.29 (2H, qm, J ) 7.0
Hz), 6.22 (1H, ddm, J ) 24.5, 17.0 Hz), 6.73 (1H, ddt, J ) 19.6,
17.0, 7.0 Hz), 7.27-7.53 (6H, m), 7.67-7.77 (4H, m); 13C NMR
(CDCl3) δ 14.0, 22.5, 27.8, 28.8, 31.5, 34.5 (d, J ) 16.4 Hz),
121.6 (d, J ) 103.4 Hz), 128.5 (d, J ) 12.3 Hz), 131.3 (d, J )
9.9 Hz), 131.6, 133.2 (d, J ) 104.2 Hz), 152.9.
Hz), 6.89-6.96 (3H, m), 7.18-7.31 (8H, m), 7.36 (1H, dm, J )
37.1, 1.5 Hz), 7.53-7.62 (4H, m); 13C NMR (CDCl3) δ 24.7 (d,
J ) 13.1 Hz), 127.5, 127.7, 128.2 (d, J ) 12.3 Hz), 129.3 (d, J
) 1.6 Hz), 129.4 (d, J ) 92.7 Hz), 131.2 (d, J ) 3.3 Hz), 131.3
(d, J ) 9.0 Hz), 132.9 (d, J ) 102.5 Hz), 135.7 (d, J ) 6.6 Hz),
145.7 (d, J ) 7.4 Hz). Anal. Calcd for C21H19OP: C, 79.23; H,
6.02. Found: C, 79.33; H, 6.03.
3-Dip h en ylp h osp h in yl-2-octen e (4f ′). Isolated as a mix-
ture of (E)- and (Z)-isomer (21:79) in 18% yield: yellow oil;
1
MS m/z 312 (M+), 201 (Ph2PO+); H NMR (CDCl3) (Z)-isomer
2-Dip h en ylp h osp h in ylst yr en e (3d ′) [3582-82-9 a n d
78045-10-0]. Isolated as a mixture of (E)- and (Z)-isomer
(76:24) in 87% yield: white solid; mp 87-89 °C; IR (Nujol) 1176
cm -1; MS m/z 304 (M+), 227 (M+ - Ph), 201 (Ph2PO+), 124
(PhPO+); 1H NMR16a δ 6.23 (0.24H, dd, J ) 19.6, 14.0 Hz,
CdC(H)P, Z-isomer), 6.76 (0.76H, dd, J ) 22.2, 17.4 Hz,
CdC(H)P, E-isomer), 7.07-7.70 (16H, m). Anal. Calcd for
(major) δ 0.75 (3H, t, J ) 7.5 Hz), 1.03-1.31 (6H, m), 1.85
(3H, d, J ) 7.0 Hz), 1.96-2.06 (2H, m), 6.51 (1H, dq, J ) 37.9,
7.0 Hz), 7.43-7.53 (6H, m), 7.67-7.81 (4H, m); (E)-isomer
(minor) (clearly assignable peaks) 0.77 (t, J ) 7.0 Hz), 1.74
(d, J ) 6.8 Hz), 6.25 (dq, J ) 21.3, 6.8 Hz).
2-Dip h en ylp h osp h in yl-3,3-d im eth yl-1-bu ten e (4g′). Iso-
lated in 8% yield: white solid; mp 133-135 °C; IR (Nujol) 1180
C
20H17OP: C, 78.93; H, 5.63. Found: C, 78.55; H, 5.34.
t
cm-1; MS m/z 284 (M+), 227 (M+ - Bu), 201 (Ph2PO+), 124
Regiochemistry of 3d ′ was confirmed by hydrogenation
(PhPO+); 1H NMR (CDCl3) δ 1.27 (9H, s), 5.20 (1H, d, J ) 22.2
Hz), 5.99 (1H, d, J ) 45.6 Hz), 7.36-7.53 (6H, m), 7.64-7.76
(4H, m); 13C NMR (CDCl3) δ 30.5 (d, J ) 8.2 Hz), 38.0 (d, J )
9.0 Hz), 127.6 (d, J ) 9.0 Hz), 128.3 (d, J ) 11.5 Hz), 131.4,
131.6 (d, J ) 9.8 Hz), 133.6 (d, J ) 105.0), 152.7 (d, J ) 87.8
Hz). Anal. Calcd for C18H21OP: C, 76.04; H, 7.44. Found: C,
76.09; H, 7.50.
[EtOH, H2 (1 atm), rt, 10 h], giving rise to 1-diphenylphos-
phinyl-2-phenylethane (81% yield): white solid; mp 68-70 °C;
IR (Nujol) 1169 cm-1; MS m/z 306 (M+), 201 (Ph2PO+), 105
(PhC2H4+); 1H NMR (CDCl3) δ 2.50 (2H, m), 2.85 (2H, m),
7.04-7.20 (5H, m), 7.37-7.47 (6H, m), 7.63-7.72 (4H, m); 13
C
NMR (CDCl3) δ 27.5 (d, J ) 3.3 Hz), 31.8 (d, J ) 70.6 Hz),
126.2, 128.0, 128.59, 128.62 (d, J ) 17.2 Hz), 130.7 (d, J ) 9.0
Hz), 131.7 (d, J ) 2.5 Hz), 132.7 (d, J ) 98.4 Hz), 141.4 (d, J
) 15.6 Hz); HRMS calcd for C20H19OP (M+) 306.1175, found
306.1196.
2-Dip h en ylp h osp h in yl-1-oct en e (4h ′). Isolated in 22%
yield: white solid; mp 140-142 °C; IR (Nujol) 1188 cm-1; MS
m/z 312 (M+), 297 (M+ - Me), 269 (M+ - Pr), 241 (M+ - Pen),
201 (Ph2PO+); 1H NMR (CDCl3) δ 0.83 (3H, t, J ) 6.8 Hz),
1.13-1.30 (6H, m), 1.42-1.52 (2H, m), 2.30 (2H, q, J ) 8.5
Hz), 5.62 (1H, d, J ) 21.0 Hz), 5.94 (1H, d, J ) 43.0 Hz), 7.45-
7.56 (6H, m), 7.68-7.73 (4H, m); 13C NMR (CDCl3) δ 14.0, 22.5,
28.0 (d, J ) 5.8 Hz), 28.9, 31.5, 31.6 (d, J ) 9.0 Hz), 128.5 (d,
J ) 12.3 Hz), 128.6 (d, J ) 10.7 Hz), 131.5 (d, J ) 101.7 Hz),
(Z)-4-Dip h en ylp h osp h in yl-4-octen e (3e′) [195148-52-8].
Isolated in 61% yield: colorless oil; IR (neat) 1188 cm-1; MS
m/z 312 (M+), 283 (M+-Et), 201 (Ph2PO+), 185 (Ph2P+); 1H NMR
(CDCl3) δ 0.65 (3H, t, J ) 7.3 Hz), 0.66 (3H, t, J ) 7.3 Hz),
1.16-1.24 (4H, m), 1.96 (2H, dt, J ) 13.8, 6.9 Hz), 2.16 (2H,
dq, J ) 3.0, 7.3 Hz), 6.29 (1H, dt, J ) 37.9, 7.3 Hz), 7.34-7.46
6562 J . Org. Chem., Vol. 68, No. 17, 2003