94
C. Grison et al. / Journal of Organometallic Chemistry 662 (2002) 83Á
/97
3
(ppm): 12.1 (s, CH2CH3), 16.4 (d, OCH2CH3, JCP
ꢀ
/
6
4.6.2.10. (3-Methyl-1-butenyl)(ethoxy)(piperidinyl)-
phosphine oxide (1cb). Compound 1cb was prepared
according to the general procedure described above
starting from 1c (2.00 g, 6.1 mmol) and isobutyralde-
hyde (0.37 g, 6.1 mmol). Compound 1cb was obtained as
an oil (1.14 g) in 76% yield and was afforded as a
3
Hz), 27.1 (d, CH2CH3, JCP
2JCP
5 Hz), 60.5 (d, OCH2, JCP
P(O)CHethyl., JCP
(s, CHarom.), 128.7 (s, CHarom.), 137.7 (s, Carom. ), 152.9
ꢀ22 Hz), 47.6 (d, NCH2,
/
2
ꢀ
/
ꢀ
/
5 Hz), 118.3 (d,
1
ꢀ
/
175 Hz), 127.3 (s, CHarom.), 128.4
2
(d, CHethyl., JCP
ꢀ
/
4 Hz).
Isomer Z: H-NMR (CDCl3) d (ppm): 0.96 (t, 3H,
CH2CH3, 3JHH
7 Hz), 1.15Á1.31 (m, 3H, OCH2CH3),
2.07Á2.21 (m, 2H, CH2CH3), 3.77Á4.13 (m, 6H, OCH2,
NCH2), 5.52Á5.70 (m, 1H, P(O)CHethyl.), 6.17Á6.56 (m,
1H, Hethyl.), 7.12Á
7.31 (m, 10H, Harom. ). 31P-NMR
1
mixture of E/Z isomers in 92/8 ratio. Rf (acetoneÁ
AcOEtÁ
hexane: 1/1/1): 0.63. IR (neat) n (cmꢂ1): 1040
(PꢀO), 1260 (PꢁO), 1623 (CꢁC).
Isomer E: H-NMR (CDCl3) d (ppm): 1.05 (d, 6H,
CH(CH3)2, 4JHP
Hz), 1.28Á1.34 (m, 3H,
OCH2CH3), 1.40Á1.65 (m, 6H, CH2), 2.35Á2.50 (m,
1H, CH(CH3)2), 2.95Á3.15 (m, 4H, NCH2), 3.93Á4.07
21
2 Hz), 6.57 (ddd, 1H, Hethyl.
/
ꢀ
/
/
/
/
/
/
/
/
1
/
/
/
ꢀ/7
/
(CDCl3) d (ppm): 19.3 (s, 1P).
/
/
/
/
2
(m, 2H, OCH2), 5.61 (ddd, 1H, P(O)CHethyl., JHP
ꢀ
/
4.6.2.8. (Dibenzylamino)(ethoxy)(2-methyl-1-
3
4
Hz, JHH
3JHP
ꢀ
/
17 Hz, JHH
ꢀ
/
,
propenyl)phosphine oxide (1bd). Compound 1bd
was prepared according to the general procedure
described above starting from 2b (2.00 g, 4.5 mmol)
and acetone (0.26 g, 4.5 mmol). Compound 1bd
was afforded in mixture with allylic subproduct 12b
in 91/9. Derivative 1bd was obtained as an oil (1.22 g)
3
3
ꢀ
/
21 Hz, JHH
ꢀ
/
17 Hz, JHH
ꢀ
6 Hz). 31P-NMR
/
(CDCl3) d (ppm): 20.2 (s, 1P). 13C-NMR (CDCl3) d
3
(ppm): 15.8 (d, OCH2CH3, JCP
ꢀ7 Hz), 20.6 (d,
/
4
CH(CH3)2, JCP
32.0 (d, CH(CH3)2, JCP
58.9Á59.2 (m, OCH2), 115.0 (d, P(O)CHethyl., JCP
175 Hz), 156.1 (s, CHethyl.).
ꢀ2 Hz), 24.2 (s, CH2), 25.8 (s, CH2),
/
3
ꢀ21 Hz), 44.2 (s, NCH2),
/
1
/
ꢀ
/
in 78% yield. Rf (acetoneÁ
IR (neat) n (cmꢂ1): 1029 (Pꢀ
(CꢁC).
1H-NMR (CDCl3) d (ppm): 1.20Á
OCH2CH3), 1.91 (s, 3H, CH3), 2.12Á
CH3), 3.88Á4.25 (m, 6H, OCH2, NCH2), 5.45Á
/
AcOEtÁ/hexane: 1/1/1): 0.64.
/
O), 1265 (Pꢁ/O), 1634
1
Isomer Z: H-NMR (CDCl3) d (ppm): 1.05 (d, 6H,
CH(CH3)2, 4JHP
Hz), 1.28Á1.34 (m, 3H,
OCH2CH3), 1.40Á1.65 (m, 6H, CH2), 2.35Á2.50 (m,
1H, CH(CH3)2), 2.95Á3.15 (m, 4H, NCH2), 3.93Á4.07
(m, 2H, OCH2), 5.40Á5.60 (m, 1H, P(O)CHethyl.), 6.12
/
ꢀ/7
/
/
1.35 (m, 3H,
2.17 (m, 3H,
5.58
/
/
/
/
/
/
/
/
(m, 1H, P(O)CHethyl.), 7.20Á
7.40 (m, 10H, Harom. ). 31P-
/
3
3
3
(ddd, 1H, Hethyl. , JHP
ꢀ
/
49 Hz, JHH
ꢀ
/
13 Hz, JHH
ꢀ
/
NMR (CDCl3) d (ppm): 19.9 (s, 1P). 13C-NMR
10 Hz). 31P-NMR (CDCl3) d (ppm): 17.8 (s, 1P).
3
(CDCl3) d (ppm): 16.4 (d, OCH2CH3, JCP
ꢀ7 Hz),
/
3
28.4 (d, CH3, JCP
2
23 Hz), 47.7 (d, NCH2, JCP
ꢀ
/
ꢀ5
/
4.6.2.11. (1-Butenyl)(ethoxy)(piperidinyl)phosphine
2
Hz), 59.9 (d, OCH2, JCP
ꢀ/6
Hz), 115.1 (d,
177 Hz), 127.3 (s, CHarom.), 128.4
(s, CHarom.), 128.8 (s, CHarom.), 137.9 (s, Carom. ), 157.6
oxide (1cg). Compound 1cg was prepared according to
the general procedure described above starting from 1c
(2.00 g, 6.1 mmol) and propanal (0.35 g, 6.1 mmol).
Compound 1cg was obtained as an oil (1.14 g) in 81%
yield and was afforded as a mixture of E/Z isomers in
1
P(O)CHethyl., JCP
ꢀ
/
2
(d, Cethyl., JCP
ꢀ6 Hz).
/
4.6.2.9. (Ethoxy)(2-phenylethenyl)(piperidinyl)-
72/28 ratio. Rf (acetoneÁ
IR (neat) n (cmꢂ1): 1040 (Pꢀ
C).
Isomer E: H-NMR (CDCl3) d (ppm): 1.07Á
3H, CH2CH3), 1.20Á1.34 (m, 3H, OCH2CH3), 1.40Á
1.64 (m, 6H, CH2), 2.18Á2.25 (m, 2H, CH2CH3),
2.95Á3.15 (m, 4H, NCH2), 3.80Á4.15 (m, 2H, OCH2),
5.57Á 6.76 (m, 1H,
/
AcOEtÁ
/
hexane: 1/1/1): 0.59.
phosphine oxide (1ca). Compound 1ca was prepared
according to the general procedure described above
starting from 1c (2.00 g, 6.1 mmol) and benzaldehyde
(0.65 g, 6.1 mmol). Compound 1ca was obtained as an
/
O), 1265 (Pꢁ
/
O), 1619 (Cꢁ
/
1
/
1.10 (m,
/
/
oil (1.43 g) in 84% yield (100% E isomer). Rf (acetoneÁ
AcOEtÁ
hexane: 1/1/1): 0.48. IR (neat) n (cmꢂ1): 1034
(PꢀO), 1259 (PꢁO), 1607 (CꢁC). MS: m/zꢀ279 [M],
280 [Mꢁ1].
Isomer E: 1H-NMR (CDCl3) d (ppm): 1.30Á
3H, CH3), 1.46Á1.65 (m, 6H, CH2), 3.05Á3.10 (m, 4H,
NCH2), 3.90Á4.20 (m, 2H, OCH2), 6.31 (dd, 1H,
/
/
/
/
/
/
/
/
/
/
5.76 (m, 1H, P(O)CHethyl.), 6.54Á
/
/
Hethyl. ). 31P-NMR (CDCl3) d (ppm): 19.8 (s, 1P). 13C-
NMR (CDCl3) d (ppm): 12.0 (s, CH2CH3), 16.2 (s,
/1.45 (m,
/
/
OCH2CH3), 24.7 (s, CH2), 26.1 (s, CH2), 27.1 (d,
3
CH2CH3, JCP
/
ꢀ
/
21 Hz), 44.7 (s, NCH2), 59.3 (d,
2
3
2
P(O)CHethyl., JHP
ꢀ
/
18 Hz, JHH
ꢀ
/
18 Hz), 7.34Á
/
7.51
OCH2, JCP
176 Hz), 151.6 (d, CHethyl., JCP
Isomer Z: 1H-NMR (CDCl3) d (ppm): 1.07Á
3H, CH2CH3), 1.20Á1.34 (m, 3H, OCH2CH3), 1.40Á
1.64 (m, 6H, CH2), 2.18Á2.25 (m, 2H, CH2CH3),
2.95Á3.15 (m, 4H, NCH2), 3.80Á4.15 (m, 2H, OCH2),
5.46Á5.69 (m, 1H, P(O)CHethyl.), 6.17Á6.49 (m, 1H,
Hethyl. ). 31P-NMR (CDCl3) d (ppm): 17.8 (s, 1P).
ꢀ
/
5 Hz), 117.4 (d, P(O)CHethyl.
,
1JCP
ꢀ
/
(m, 6H, Harom. , Hethyl. ). 31P-NMR (CDCl3) d (ppm):
19.6 (s, 1P). 13C-NMR (CDCl3) d (ppm): 16.1 (br s,
ꢀ4 Hz).
/
2
/1.10 (m,
3
OCH2CH3), 24.5 (s, CH2), 26.1 (d, CH2, JCP
ꢀ
/
5 Hz),
5 Hz),
176 Hz), 127.3 (s,
CHarom.), 128.8 (s, CHarom.), 129.5 (s, CHarom.), 134.2
/
/
2
44.5Á
/
44.6 (m, NCH2), 59.6 (d, OCH2, JCP
ꢀ
/
/
116.5 (d, P(O)CHethyl.
,
1JCP
ꢀ
/
/
/
/
/
2
(s, Carom. ), 145.4 (d, CHethyl., JCP
ꢀ5 Hz).
/