C. Grison et al. / Tetrahedron 59 (2003) 2101–2123
2113
2
5JH – P¼2.0 Hz, 1H, CvCH–(CH2)5 –CH3]; 13C NMR
(CDCl3): dC¼13.8 [CvCH–(CH2)5–CH3], 14.1 [CH3–
CH2–CH2–CvCH], 21.4 [CH3–CH2–CH2–CvCH], 22.4
[CvCH–(CH2)4 –CH–CH3], 27.5, 28.9, 29.8, 31.5
[CvCH–(CH2)4 –CH2 –CH3], 38.0 [CH3 –CH2 –CH2 –
CvCH], 36.7–37.0 [[(CH3)2N]2PO and CH3 –N–
CH2Ph), 34.8 (CvCH–CH2–CH2Ph), 36.1 [d, JC–P
¼
3.7 Hz, [(CH3)2N]2PO and CH3–N–C(Me)vCH], 124.9,
127.4, 127.6 (C 2, C 3, C 4 of Ph), 125.2 (CvCH–CH2–
CH2Ph), 137.8 (C 1 of Ph), 141.2 (CvCH–CH2–CH2Ph);
31P NMR (101.256 MHz, CDCl3): dP¼19.38.
3
C(Me)vCH], 123.4 [d, JC–P¼4.0 Hz, CvCH–(CH2)5–
4.7.8. [(1-Pheny-3-hepten-4-yl)]pentamethyl phosphoric
triamide 5be. Yield: 100% (Z/E: 100/0); yellow oil; IR
(NaCl plates, cm21): nmax¼3063, 3027, 3000, 2958, 2929,
2805, 1663, 1603, 1454, 1376 and 1297; 1H NMR (CDCl3):
dH¼0.92 (t, 3JH–H¼7.5 Hz, 3H, CH3–CH2–CH2–CvCH),
CH3], 142.3 (CvCH–(CH2)5 –CH3); 31P NMR
(101.256 MHz, CDCl3): dP¼19.51.
4.7.6. [(1-phenyl-1-octen-1-yl)]pentamethyl phosphoric
triamide 5cd. Yield: 75% (Eþ¼PeCl), 78% (Eþ¼PeI); pale
yellow oil; isomer Z only; IR (NaCl plates, cm21):
nmax¼2924, 2802, 1638 and 1297; 1H NMR (CDCl3):
dH¼0.83–0.96 [m, 3H, CvCH–(CH2)5–CH3], 1.25–1.48
[m, 6H, CvCH–CH2–CH2–(CH2)3–CH3], 1.75–1.86 [m,
2H, CvCH–CH2–CH2–(CH2)3–CH3], 2.33–2.41 [m, 2H,
CvCH–CH2–(CH2)4–CH3], 2.54 [d, 3JH–P¼9.0 Hz, 12H,
3
3
1.49 (m, JH–H¼7.5 Hz and JH–H¼7.5 Hz, 2H, CH3–
3
CH2–CH2–CvCH), 2.14 (t, JH–H¼7.5 Hz, 2H, CH3–
CH2–CH2–CvCH), 2.41–2.51 (m, 2H, CvCH–CH2–
CH2Ph), 2.64–2.73 (m, 2H, CvCH–CH2–CH2Ph), 2.64
3
3
[d, JC–P¼9.1 Hz, 12H, [(CH3)2N]2PO], 2.65 [d, JC–P
¼
3
8.0 Hz, 3H, CH3–N–C(Pr)vCH], 5.17 (t, JH–H¼6.9 Hz,
1H, CvCH–CH2–CH2Ph), 7.17–7.30 (m, 5H, Ph); 13C
NMR (CDCl3): dC¼13.6 (CH3–CH2–CH2–CvCH), 20.5
(CH3–CH2–CH2–CvCH), 29.2 (CvCH–CH2–CH2Ph),
3
[(CH3)2N]2PO], 2.93 [d, JH–P¼8.5 Hz, 3H, CH3–N–
3
C(Ph)vCH], 5.71 [d, JH–H¼7.2 Hz, 1H, CvCH–CH2–
(CH2)4–CH3], 7.26–7.52 (m, 5H, Ph); 13C NMR (CDCl3):
dC¼13.9 [CvCH–(CH2)5–CH3], 22.4 [CvCH–(CH2)4–
CH2–CH3], 28.2, 29.2, 29.3, 31.6 [CvCH–(CH2)4–CH2–
35.4 (CvCH–CH2–CH2Ph), 36.4 [d, JC–P¼3.7 Hz,
2
CH3–N–C(Pr)vCH],
36.6
[(CH3)2N]2PO], 37.8 (CH3–CH2–CH2–CvCH), 124.0
[d,
2JC–P¼3.7 Hz,
2
3
CH3], 36.8 [d, JC–P¼3.6 Hz, [(CH3)2N]2PO], 37.4 [d,
(d, JC–P¼6.1 Hz, CvCH–CH2–CH2Ph), 125.4, 127.9,
2JC–P¼3.9 Hz, CH3–N–C(Ph)vCH], 126.1, 127.0, 127.9,
128.1 (C 2, C 3, C 4 of Ph), 141.7 (C 1 of Ph), 142.6
(CvCH–CH2–CH2Ph); 31P NMR (101.256 MHz, CDCl3):
dP¼17.92; MS (EIþ) m/z calculated for C18H32N3OP [M]þ
337.4 found 338 [[Mþ1]þ, 65%], 246 [[M2CH2Ph]þ,
90%], 202 [[M2(Me2N)2PO]þ, 28%], 135 [[(Me2N)2PO]þ,
100%].
128.8, 128.9 [CvCH–(CH2)5–CH3 and C 2, C 3, C 4 of Ph],
2
140.6 (C 1 of Ph), 142.16 [d, JC–P¼1.9 Hz, C(Ph)vCH–
(CH2)5–CH3]; 31P NMR (101.256 MHz, CDCl3): dP¼
17.90; MS (EIþ) m/z calculated for C19H34N3OP [M]þ
351.5 found 351 [[M]þ, 48%], 336 [[M2CH3]þ, 14%], 216
[[M2(Me2N)2PO]þ, 100%], 135 [[(Me2N)2PO]þ, 92%], 77
[[Ph]þ, 25%], 44 [[(Me2)N]þ, 71%].
4.7.9. [(1,4-Diphenyl-1-buten-1-yl)]pentamethyl phos-
phoric triamide 5ce. Yield: 98%; Z/E: 100/0; yellow oil;
IR (NaCl plates, cm21): nmax¼3026, 2924, 1636, 1600,
1492, 1453 and 1299; 1H NMR (CDCl3): dH¼2.50 [d,
3JH–P¼9.1 Hz, 12H, [(CH3)2N]2PO], 2.69–2.77 (m, 2H,
CvCH–CH2–CH2Ph), 2.77–2.84 (m, 2H, CvCH–CH2–
CH2Ph), 2.82 [d, 3JH–P¼8.6 Hz, 3H, CH3–N–C(Ph)vCH],
4.7.7. [(5-Phenyl-2-penten-2-yl)]pentamethyl phosphoric
triamide 5ae. Yield: 97% (Z/E: 90/10); yellow oil; IR
(NaCl plates, cm21): nmax¼3026, 2920, 2804, 1670, 1603,
1495, 1454, 1375 and 1297; MS (EIþ) m/z calculated for
C16H28N3OP [M]þ 309.4 found 309 [[M]þ, 6%], 218
[[M2CH2Ph]þ, 86%], 135 [[(Me2N)2PO]þ, 100%], 91
[[CH2Ph]þ, 40%].
3
5.72 (t, JH–H¼6.8 Hz, 1H, CvCH–CH2–CH2Ph), 7.17–
7.48 (m, 10H, 2£Ph); 13C NMR (CDCl3): dC¼30.1
(CvCH–CH2–CH2–Ph), 35.6 (CvCH–CH2–CH2–Ph),
2
2
Z isomer: 1H NMR (CDCl3): dH¼1.84–1.85 [m, 3H, CH3–
C(N)vCH–CH2–CH2Ph], 2.39–2.50 (m, 2H, CvCH–
36.9 [d, JC–P¼3.7 Hz, [(CH3)2N]2PO], 37.3 [d, JC–P¼
3.7 Hz, CH3–N–C(Ph)vCH], 125.8, 126.3, 127.2, 128.0,
128.3, 128.5, 140.5, 141.7 (2£Ph), 142.9 (d, 3JC–P¼2.4 Hz,
CvCH–CH2–CH2–Ph); 31P NMR (101.256 MHz,
CDCl3): dP¼17.83; MS (EIþ) m/z calculated for
C21H30N3OP [M]þ 371.5 found 371 [[M]þ, 8%], 280
[[M2CH2Ph]þ, 53%], 235 [[M2(Me2N)2PO]þ, 18], 135
[[(Me2N)2PO]þ, 100%], 91 [[CH2Ph]þ, 25%].
3
CH2 –CH2Ph), 2.62 [d, JH – P¼8.7 Hz, 3H, CH3 –N–
C(Me)vCH), 2.64–2.69 (m, 2H, CvCH–CH2–CH2Ph),
2.65 [d, JH – P¼9.1 Hz, 12H, [(CH3)2N]2PO], 5.21
3
3
(t, JH – H¼6.9 Hz, 1H, CvCH–CH2 –CH2Ph), 7.17–
7.33 (m, 5H, Ph); 13C NMR (CDCl3): dC¼20.3
[CH3C(N)vCH–CH2 –CH2Ph], 28.7 (CvCH–CH2 –
CH2Ph), 34.8 (CvCH–CH2–CH2Ph), 36.1 [d, JC–P
2
¼
3.7 Hz, [(CH3)2N]2PO and CH3–N–C(Me)vCH], 124.9,
127.4, 127.6 (C 2, C 3, C 4 of Ph), 125.2 (CvCH–CH2–
CH2Ph), 137.8 (C 1 of Ph), 141.2 (CvCH–CH2–CH2Ph);
31P NMR (101.256 MHz, CDCl3): dP¼17.97.
4.7.10. [(5-Methyl-2-hexen-2-yl)]pentamethyl phos-
phoric triamide 5af. Yield: 100% (Z/E: 80/20); yellow
oil; IR (NaCl plates, cm21): nmax¼2897, 2842, 2805, 1669,
1460, 1377 and 1298; MS (EIþ) m/z calculated for
C12H28N3OP [M]þ 261.3 found 261 [[M]þ, 19%], 218
[[M2iPr]þ, 58%], 135 [[(Me2N)2PO]þ, 100%], 126
[[M2(Me2N)2PO]þ, 52%].
E isomer: 1H NMR (CDCl3): dH¼1.80–1.82 [m, 3H, CH3–
C(N)vCH–CH2–CH2Ph], 2.39–2.50 (m, 2H, CvCH–
CH2 –CH2Ph), 2.62 [d, JH – P¼8.7 Hz, 3H, CH3 –N–
3
1
3
C(Me)vCH), 2.64–2.69 (m, 2H, CvCH–CH2–CH2Ph),
3
Z isomer: H NMR (CDCl3): dH¼0.90 [d, JH–H¼6.7 Hz,
6H, CvCH–CH2 –CH(CH3)2], 1.53–1.69 [m, 1H,
CvCH–CH2 –CH(CH3)2], 1.85–1.86 [m, 3H, CH3 –
C(N)vCH], 1.96–2.03 [m, 2H, CvCH–CH2 –
CH(CH3)2], 2.67 [d, JH–P¼9.5 Hz, 12H, [(CH3)2N]2PO],
2.65 [d, JH – P¼9.1 Hz, 12H, [(CH3)2N]2PO], 5.04
3
(t, JH–H¼7.3 Hz, 1H, CvCH–CH2–CH2Ph), 7.17–7.33
(m, 5H, Ph); 13C NMR (CDCl3): dC¼20.3
3
[CH3C(N)vCH–CH2 –CH2Ph], 28.7 (CvCH–CH2 –