3206
E. Sierecki et al.
PAPER
Anal. Calcd for C16H22Cl2NO4P: C, 48.75; H, 5.62; N, 3.55. Found:
C, 48.46; H, 5.64; N, 3.51.
13C NMR (75 MHz, CDCl3): d = 151.5, 135.2, 129.7, 124.4, 120.3,
115.8, 78.7, 55.6, 47.2, 43.0, 40.6, 34.4, 33.2, 31.8, 26.5, 25.6, 23.2
(major), 22.3 (minor), 21.3, 15.9.
31P NMR (125 MHz, CDCl3): d = 3.8 (major), 3.7 (minor), 3.0 (ma-
jor), 2.6 (minor).
1-[4-(2,6-Difluorophenyl)-5,5-dimethyl-2-oxo-2l5-1,3,2-dioxa-
phosphinan-2-yl]-2-methoxypyrrolidine (8d)
The reaction was stopped once 405 C (4.2 F·mol–1) had been con-
sumed.
MS (CI): m/z = 428 [M + Na]+.
Yield: 350 mg (97%); white solid.
Menthyl Phenyl(2-allylpyrrolidin-1-yl)phosphinate (10)
The major methoxy derivative 7 (Rf = 0.33) was used as starting ma-
terial.
Rf = 0.56 (Et2O–MeOH, 97:3).
1H NMR (400 MHz, CDCl3): d = 7.28 (m, 1 H), 6.91 (d, J = 9.0 Hz,
1 H), 6.87 (d, J = 9.0 Hz, 1 H), 5.91 (d, J = 2.0 Hz, 1 H), 5.11 (m, 1
H), 4.47 (dd, J = 3.0, 11.0 Hz, 1 H), 3.83 (dd, J = 11.0, 24.0 Hz, 1
H), 3.44 (m, 2 H), 3.33 (s, 3 H, 1st dia), 3.30 (s, 3 H, 2nd dia), 2.04
(m, 1 H), 1.92 (m, 2 H), 1.78 (m, 1 H), 1.16 (s, 3 H), 0.78 (s, 3 H).
13C NMR (75 MHz, CDCl3): d = 160.7 (dd, 1J = 305 Hz, 3J = 28.0
Hz), 130.3, 130.2, 111.9 (m), 91.5, 78.5, 76.3, 55.4, 46.7, 36.5, 33.5,
26.4, 20.6, 18.8.
Yield: 143 mg (84%); transparent oil.
Rf
= 0.58 (major), 0.21 (minor) (heptane–EtOAc–MeOH:
48.5:48.5:3).
1H NMR (400 MHz, CDCl3, major): d = 7.66 (t, 2 H), 7.33 (m, 3 H),
5.69 (m, 1 H), 5.00 (m, 2 H), 4.25 (m, 1 H), 3.62 (m, 1 H), 3.29 (m,
1 H), 3.14 (m, 1 H), 2.45 (m, 2 H), 2.31 (m, 1 H), 2.15 (m, 1 H), 1.98
(m, 1 H), 1.78 (m, 1 H), 1.64 (m, 2 H), 1.50 (m, 2 H), 1.33 (m, 4 H),
0.98–0.87 (m, 10 H).
13C NMR (75 MHz, CDCl3): d = 131.9, 130.6, 128.3, 127.7, 115.2,
76.7, 55.3, 47.0, 43.4, 40.4, 34.2, 33.2, 31.8, 26.7, 25.8, 25.6, 22.0,
21.4, 15.9.
31P NMR (125 MHz, CDCl3): d = 4.0, 3.9.
MS (CI): m/z = 384 [M + Na]+.
1-{4-[2-Fluoro-6-(trifluoromethyl)phenyl]-5,5-dimethyl-2-oxo-
2l5-1,3,2-dioxaphosphinan-2-yl}-2-methoxypyrrolidine (8e)
The reaction was stopped once 1351 C (14.0 F·mol–1) had been con-
sumed.
MS (CI): m/z = 412 [M + Na]+.
2-Allyl-1-(5,5-dimethyl-2-oxo-4-phenyl-2l5-1,3,2-dioxaphos-
phinan-2-yl)pyrrolidine (11a)
Yield: 395 mg (96%); transparent oil.
Yield: 140 mg (95%); white solid.
Rf = 0.60 (Et2O–MeOH, 97:3).
Rf = 0.42 (Et2O–MeOH, 96:4).
1H NMR (400 MHz, CDCl3): d = 7.55–7.40 (m, 2 H), 7.32 (m, 1 H),
5.89 (d, J = 2.0 Hz, 1 H), 5.08 (m, 1 H), 4.35 (dd, J = 2.0, 11.0 Hz,
1 H), 3.98 (dd, J = 11.0, 24.0 Hz, 1 H), 3.42 (m, 1 H), 3.33 (s, 3 H,
1st dia), 3.30 (s, 3 H, 2nd dia), 3.30 (m, 1 H), 2.04 (m, 1 H), 1.86
(m, 2 H), 1.75 (m, 1 H), 1.17 (s, 3 H, 1st dia), 1.11 (s, 3 H, 2nd dia),
0.94 (s, 3 H).
IR (neat): 3068, 2975, 2880, 1640, 1495, 1475, 1454, 1367, 1256,
1125, 1056, 927 cm–1.
1H NMR (400 MHz, CDCl3): d = 7.32 (m, 3 H), 7.24 (m, 2 H), 5.81
(m, 1 H), 5.43 (d, J = 2.0 Hz, 1 H, major), 5.41 (d, J = 2.0 Hz, 1 H,
minor), 5.04 (m, 2 H), 5.01 (m, 1 H), 4.49 (dd, J = 11.0, 2.0 Hz, 1
H), 3.92 (dd, J = 11.0, 23.0 Hz, 1 H), 3.46 (m, 1 H), 3.37 (m, 1 H),
2.55 (m, 1 H), 2.21 (m, 2 H), 1.90 (m, 2 H), 1.76 (m, 1 H), 1.00 (s,
3 H), 0.75 (s, 3 H).
13C NMR (75 MHz, CDCl3): d = 162.0 (d, 1J = 254 Hz), 131.6 (d,
3J = 10.0 Hz), 131.5 (m), 124.0 (q, 1J = 221 Hz), 122.7 (q, 2J = 10.0
2
Hz), 122.2, 121.2 (d, J = 25.0 Hz), 91.1/91.0, 80.3, 77.4, 54.8,
45.5, 37.1, 33.2/33.1, 23.4, 22.8/22.4, 20.8.
31P NMR (125 MHz, CDCl3): d = 3.6, 3.2.
MS (CI): m/z = 434 [M + Na]+.
13C NMR (75 MHz, CDCl3): d = 136.6, 135.1, 128.1, 127.7, 127.3,
117.2, 85.0, 76.7, 58.4, 47.2, 40.8 (major), 40.5 (minor), 35.6, 30.5,
24.9, 21.2, 17.6.
31P NMR (300 MHz, CDCl3): d = 5.74 (minor), 5.67 (major).
MS (CI): m/z = 358, 359 [M + Na]+.
2-Allylpyrrolidines 9, 10, and 11a–e by Allylation of 2-Meth-
oxypyrrolidines 6, 7, and 8a–e ; General Procedure
Anal. Calcd for C18H26NO3P: C, 64.46; H, 7.81; N, 4.18. Found: C,
64.32; H, 7.99; N, 4.04.
A soln of 2-methoxypyrrolidine 6, 7, or 8a–e (0.440 mmol) in
CH2Cl2 (15 mL) was placed in a three-neck flask under argon and
cooled at –78 °C. BF3·OEt2 (111 mL, 0.875 mmol) was slowly add-
ed by syringe. The mixture was allowed to react for 15 min before
allyltrimethylsilane (94 mL, 0.594 mmol) was added. The acetone–
dry ice bath was allowed to warm to r.t. overnight, and the reaction
took place over 15 h. The reaction was quenched with diluted aq
NH3. The layers were separated. The aqueous layer was extracted
with CH2Cl2 (2 × 20 mL) and the combined organic layers were
washed with brine (2 × 20 mL) and processed by the standard pro-
cedure. The products were separated by column chromatography
(silica gel; heptane–EtOAc, 1.5:1).
2-Allyl-1-[4-(2,4-dichlorophenyl)-5,5-dimethyl-2-oxo-2l5-1,3,2-
dioxaphosphinan-2-yl]pyrrolidine (11b)
Yield: 165 mg (93%); white solid.
Rf = 0.51 (Et2O–MeOH, 97:3).
IR (neat): 3074, 2972, 2882, 1734, 1640, 1590, 1562, 1471, 1436,
1363, 1259, 1206, 1105, 1044, 920 cm–1.
1H NMR (400 MHz, CDCl3): d = 7.34 (d, J = 5.0 Hz, 1 H), 7.33 (s,
1 H), 7.23 (d, J = 6.0 Hz, 1 H), 5.93 (d, J = 2.0 Hz, 1 H, major), 5.91
(d, J = 2.0 Hz, 1 H, minor), 5.74 (m, 1 H), 5.02 (m, 2 H), 4.51 (dd,
J = 2.0, 11.0 Hz, 1 H), 3.86 (m, 1 H), 3.79 (dd, J = 11.0, 25.0 Hz, 1
H), 3.42 (m, 1 H), 3.30 (m, 1 H), 2.46 (m, 1 H), 2.29 (m, 2 H), 1.88
(m, 2 H), 1.72 (m, 1 H), 1.05 (s, 3 H), 0.79 (s, 3 H).
13C NMR (75 MHz, CDCl3): d = 135.0, 134.6, 133.7, 130.5, 129.2,
126.8, 79.8, 76.5, 58.5, 47.2, 40.7 (major), 40.5 (minor), 37.0, 30.5,
29.7, 24.8, 20.9, 18.2.
Menthyl Phenyl(2-allylpyrrolidin-1-yl)phosphonate (9)
Yield: 155 mg (87%); transparent oil.
Rf = 0.25 (heptane–EtOAc, 1.5:1).
1H NMR (300 MHz, CDCl3): d = 7.30 (m, 4 H), 6.95 (t, J = 8.0 Hz,
1 H), 5.82 (m, 1 H), 5.03 (m, 2 H), 4.27 (m, 1 H), 3.76 (m, 1 H), 3.41
(m, 1 H), 3.28 (m, 1 H), 3.12 (m, 1 H), 2.50 (m, 1 H), 2.18 (m, 3 H),
2.01 (m, 1 H), 1.81 (m, 2 H), 1.61 (m, 4 H), 1.39–0.91 (m, 3 H),
0.90–0.66 (m, 9 H).
31P NMR (125 MHz, CDCl3): d = 4.7 (minor), 4.5 (major).
MS (CI): m/z = 426, 428 [M + Na]+.
Synthesis 2006, No. 19, 3199–3208 © Thieme Stuttgart · New York