8
PRISHCHENKO Et al.
|
3.36 (s, 3H, CH3O), 3.8-4.0 (m, 4H, 2 CH2OP). 13C NMR
Me3Si), 23.7 (s, C4), 29.3 (s, C5), 45.1 (s, C3), 51.1 (s, CH3O),
1
1
1
(CDCl3, δ): 12.73 (d, JPC=121.9 Hz, MeP), 16.4-16.6 (m,
52.3 (d, JPC=111.8 Hz, C1), 66.1 (d, JPC=10.9 Hz, C2),
173.6 (s, C6). 31P NMR (CDCl3, 162 MHz) δ, ppm: 38.6 (s).
Anal. Calcd for C17H33N2O6PSi. C, 48.55; H, 7.91. Found:
C, 48.23; H, 7.80.
2 CH3), 23.7 (s, C4), 29.1 (s, C5), 51.21 (s, MeO), 53.2 (d,
1JPC=111.7 Hz, C1), 55.0 (d, JPC=11.7 Hz, C3), 59.8-60.0
3
(m, 2 CH2OP), 66.6 (d, 3JPC=12.3 Hz, C2), 173.6 (s, C6). 31
P
NMR (CDCl3, 162 MHz) δ, ppm: 48.9 (s). Anal. Calcd for
C10H20NO4P. C, 48.19; H, 8.09. Found: C, 48.02; H, 7.95.
4.18
Trimethylsilyl [(2-(methoxycarbonyl)
|
pyrrolidin-1-yl)methyl]phosphonite (19)
4.15
Methyl 1-(1,4,6,9-tetraoxa-5-
|
Ether 4a (11.2 g, 0.06 mol) was added drop wise to the
solution of bis(trimethylsiloxy)phosphine (16.1 g, 0.077
mol) in methylene chloride (50 mL) under stirring and
cooling to 10°C. The solvent was removed, the resi-
due was distilled to give 13.9 g of phosphonite 19, yield
phosphaspiro[4.4]non-5-ylmethyl)prolinate (16)
A mixture of 1,4,6,9-tetraoxa-5-phosphaspiro[4.4]nonane
(4.8 g, 0.032 mol), methyl ether 4a (5.2 g, 0.03 mol), and
zinc chloride (0.1 g) was heated under 100-120°C with
methanol distillation. The residue was distilled to give 6.5 g
of spirophosphorane 16, yield 74%, bp 168°C (2 mm Hg).
1H NMR (CDCl3, 400 MHz) δ, ppm: 3.40 (m ABX, 2H,
2JHH=15.8 Hz, 2JPH=4.5 Hz, C1H2), the second part of ABX
system, C1H and spirophosphorane moieties coincided, 3.6-
4.0 (m, 16H, 4 OCH2CH2OP). 13C NMR (CDCl3, 100 MHz)
1
83%, bp 142°C (2 mm Hg). H NMR (CDCl3, 400 MHz)
δ, ppm: 0.15 (s, 9H, Me3Si), 2.71 and 3.01 (m ABX, 2H,
2JHH=14.8 Hz, 2JPH=9.2 Hz, 2JPH=11.2 Hz, C1H2), 3.24 (dd,
1H, JHH=7.2 Hz, JHH=5.6 Hz, C2H), 3.35 (s, 3H, CH3O),
3
3
7.15 (dt, 1H, JPH=548.7 Hz, JHH=1.6 Hz, HP). 13C NMR
(CDCl3, 100 MHz) δ, ppm: 0.97 (s, Me3Si), 23.6 (s, C4),
28.9 (s, C5), 51.18 (s, CH3O), 54.4 (d, 1JPC=114.3 Hz, C1H2),
1
3
δ, ppm: 54.1 (d, JPC=179.2 Hz, C1), 54.4 (d, JPC=2.9 Hz,
C3), 65.1 (d, 3JPC=10.4 Hz, C2), 174.3 (d, 4JPC=2.9 Hz, C6),
59.0-61.0 (m, 4 OCH2CH2OP). 31P NMR (CDCl3, 162 MHz)
δ, ppm: −9.4 (s). Anal. Calcd for C11H20NO6P. C, 45.05; H,
6.87. Found: C, 44.91; H, 6.72.
1
3
54.7 (d, JPC=2.8 Hz, C3), 174.6 (s, C6). 31P NMR (CDCl3,
3
162 MHz) δ, ppm: 17.7 (s). Anal. Calcd for C10H22NO4PSi.
C, 42.30; H, 7.94. Found: C, 42.12; H, 7.86.
4.19
Trimethylsilyl [(2-(methoxycarbonyl)
|
4.16
Diethyl [(2-(methoxycarbonyl)
pyrrolidin-1-yl)methyl][3-(trimethylsilyloxy)-3-
oxopropyl]phosphinate (20)
|
pyrrolidin-1-yl)methyl]phosphonite (17)
A mixture of O,O-diethyl pivaloylphosphonite (4.8 g, 0.023
mol), ether 4b (5.3 g, 0.028 mol), ethanol (2 mL), and boron
fluoride etherate (0.3 g) was kept at 70°C and was distilled to
give 4 g of phosphonite 17, yield 66%, bp 103°C (1 mm Hg).
1H NMR (CDCl3, 400 MHz) δ, ppm: 1.0-1.1 (m, 6H, 2 CH3),
2.7-3.0 (m ABX, 2H, C1H2), 3.4-3.6 (m, 2H, C1H2), 3.47 (s,
3H, CH3O), 3.7-3.9 (m, 4H, 2 CH2OP). 13C NMR (CDCl3,
100 MHz) δ, ppm: 17.2-17.5 (m, 2 CH3), 23.8 (s, C4), 29.1
Trimethylsilyl acrylate (6 g, 0.042 mol) was added to the solu-
tion of phosphonite 19 (5.8 g, 0.021 mol) in methylene chlo-
ride (10 mL) and pyridine (2 mL). The solvent was removed,
the residue was kept at 100°C for 1 hour, and distilled to
give 7 g of phosphinate 20, yield 79%, bp 180°C (2 mm
1
Hg). The first isomer, 60%. H NMR (CDCl3, 400 MHz) δ,
ppm: 0.1-0.16 (m, 18H, 2 Me3Si), 2.68 and 3.08 (m ABX,
2
2
2
2H, JHH=14.0 Hz, JPH=9.0 Hz, JPH=14.0 Hz, C1H2),
(s, C5), 51.0 (s, CH3O), 54.9 (d, JPC=5.0 Hz, C3), 56.6 (d,
3.26 (dd, 1H, JHH=8.6 Hz, JHH=5.4 Hz, C2H), the signals
of protons of pyrrolidine and propionic moieties coincided.
13C NMR (CDCl3, 100 MHz) δ, ppm: −0.2 to 1.2 (m, Me3Si,
Me3SiOP), 23.4 (s, C4), 28.0 (d, 1JPC=97.6 Hz, C7), 28.9 (d,
2JPC=1 Hz, C8), 29.0 (s, C5), 54.2 (d, 1JPC=122.4 Hz, C1), 54.9
1
3
3
1JPC=9.9 Hz, C2), 62.1 (d, 1JPC=9.9 Hz, C1), 62.0-63.5 (m, 2
CH2O), 173.1 (s, C6). 31P NMR (CDCl3, 162 MHz) δ, ppm:
170.4 (s). Anal. Calcd for C, 50.18; H, 8.42. C11H22NO4P.
Found: C, 50.32; H, 8.36.
(d, JPC=2.8 Hz, C3), 67.7 (d, JPC=14.4 Hz, C2), 173.3 (d,
3JPC=1 Hz, C9), 173.6 (s, C6). 31P NMR (CDCl3, 162 MHz)
δ, ppm: 39.1 (s). The second isomer, 40%. 1H NMR (CDCl3,
400 MHz) δ, ppm: 0.1-0.16 (m, 18H, 2 Me3Si), 2.72 and 3.12
3
3
4.17
Trimethylsilyl [(2-(methoxycarbonyl)
|
pyrrolidin-1-yl)methyl]phosphinate (18)
2
2
2
The mixture bis(trimethylsiloxy)phosphine (5.7 g, 0.027
mol), aminale 5 (18.4 g, 0.069 mol), and zinc chloride (0.2 g)
was kept at 120°C for 2 hour, and then was distilled to give
10.2 g of phosphinate 18, yield 93%, bp 183°C (0.5 mm Hg).
1H NMR (CDCl3, 400 MHz) δ, ppm: 0.29 (s, 9H, Me3Si),
2.6-3.3 (m ABX, 2H, C1H2), 3.4-3.6 (m, 2H, C1H2), 3.48 (s,
6H, 2 CH3O). 13C NMR (CDCl3, 100 MHz) δ, ppm: 1.34 (s,
(m ABX, 2H, JHH=14.0 Hz, JPH=9.0 Hz, JPH=14.0 Hz,
C1H2), 3.28 (dd, 1H, JHH=8.6 Hz, JHH=5.4 Hz, C2H), the
signals of protons of pyrrolidine and propionic moieties coin-
cided. 13C NMR (CDCl3, 100 MHz) δ, ppm: −0.2 to 1.2 (m,
3
3
Me3Si, Me3SiOP), 23.5 (s, C4), 28.0 (d, JPC=99.3 Hz, C7),
1
28.9 (s, C5), 29.0 (d, 2JPC=1 Hz, C8), 54.3 (d, 1JPC=124.3 Hz,
C1), 54.9 (d, JPC=3.0 Hz, C3), 67.7 (d, JPC=14.2 Hz, C2),
3
3