8824
M. Maffei, G. Buono / Tetrahedron 59 (2003) 8821–8825
3
1
1
2
37.12 and 137.22 (Carom.). 1P NMR: 22.9. IR (cm21):
Found: C 64.01; H 6.31. H NMR: 3.58–3.73 (OCH , m);
2
870, 2450, 1280, 1120. a (258C)¼266.4 (c¼2.8, CH Cl ).
4.45–4.62 (CH–O and PhCH O, m); 5.79–6.69 (3H, m);
2
D
2
2
1
3
3
7
.16–7.30 (10H, m). C NMR: 69.28 (OCH , d, J ¼
2
PC
3
2 PC 2
1
.1.4. 2-Oxo-1,3,2-dioxaphosphorinane (Id). Bp 1208C
0.6 Torr). Anal. calcd (C H O P): C 29.51; H 5.74. Found:
5.5 Hz); 69.92 (OCH , d, J ¼5 Hz); 73.51 (PhCH O, s);
2
2 PC
(
C 30.13; H 6.20. H NMR: 1.73–2.32 (CH , m); 3.37–4.59
73.66 (PhCH O, s); 78.45 (CH–O, d, J ¼24.8 Hz);
PC
3
7
3
1
1
124.32 (vCH–P, d, J ¼158.8 Hz); 127.68, 127.92,
2
13
1
(
(
OCH , m); 6.93 (1H d, J ¼675 Hz). C NMR: 27.95
128.36, 133.30 and 133.65 (Carom.); 137.91 (vCH , s).
2
2
PH
3
2
31
31
21
CH , d, J ¼8.1 Hz); 67.51 (OCH , d, J ¼6.3 Hz).
P
P NMR: 33.2. IR (cm ): 3060, 2940, 2900, 1615, 1270,
1050. a (258C)¼238.3 (c¼3.2, CH Cl ).
2
PC
2
PC
2
1
NMR: 2.4. IR (cm ): 2970, 2900, 2430, 1470, 1260.
D
2
2
1
(
4
.1.5. 5,5-Dimethyl-2-oxo-1,3,2-dioxaphosphorinane
Ie). Bp 1208C (0.02 Torr). Anal. calcd (C H O P): C
1.2.4. 2-Oxo-2-vinyl-1,3,2-dioxaphosphorinane (IId). Bp
1058C (0.3 Torr). Anal. calcd (C H O P): C 40.54; H 6.08.
5
11
3
5 9 3
1
1
0.00; H 7.33. Found: C 40.07; H 7.40. HNMR: 0.90 (CH ,
3
Found: C 40.86; H 5.87. H NMR: 1.75–2.42 (CH , m);
2
1
13
s); 1.22 (CH , s); 4.00 (4H, m); 6.87 (1H, d, J ¼675 Hz).
3.95–4.32 (OCH , m); 5.89–6.75 (3H, m). C NMR: 26.32
2
3
PH
1
3
3
3
2
CNMR: 20.66 (CH , s); 21.72 (CH , s); 32.15 (Me C, d,
3
(CH , d, J ¼8.1 Hz); 67.62 (OCH , d, J ¼6.5 Hz);
3
2
2
PC
2
PC
2
31
1
J ¼6.3 Hz); 76 (CH , d, J ¼6.3 Hz). P NMR: 3.3. IR
124.91 (vCH–P, d, J ¼177.5 Hz); 135.68 (vCH , s).
PC
2
2
PC
PC
21
2
1
31
(
cm ): 2970, 2880, 2410, 1730, 1260.
P NMR: 10.1. IR (cm ): 2980, 2900, 1630, 1240, 1160.
1.2. General procedure for the preparation of cyclic
vinyl phosphonates
1.2.5. 5,5-Dimethyl-2-oxo-2-vinyl-1,3,2-dioxaphosphori-
nane (IIe). White solid, mp 878C (ethyl acetate/hexane,
1
:1). Anal. calcd (C H O P): C 47.73; H 7.39. Found: C
7 13 3
1
A mixture of palladium tetrakis(triphenyl phosphine) (1.5 g;
1
47.84; H 7.32. H NMR: 1.04 (CH , s); 1.07 (CH , s); 3.84
3 3
(OCH , t, J ¼11.2 Hz); 4.13 (OCH , t, J ¼11.1 Hz);
5.90–6.62 (3H, m). C NMR: 20.99 (CH , s); 21.25 (CH ,
3 3
3
3
.3 mmol), cyclic phosphite (100 mmol), triethylamine
10 g; 99 mmol), vinyl bromide (14 g; 131 mmol) and
2
PH
2
PH
1
3
(
3
2
toluene (30 mL) was heated to 708C (for six-membered
compounds) or 90–1008C (for five-membered analogues)
with stirring under a nitrogen atmosphere in a thick wall
Schlenck tube. A white precipitate appeared, and the
reaction mixture then turned to a viscous mass, which
characterizes the end of the reaction. The tube was cooled to
room temperature, ethyl acetate (50 mL) was added, and the
suspension was filtered. The solid was washed with ethyl
acetate (4£30 mL) and the combined filtrates were evapo-
rated in vacuo. The residue was passed over a short silica
column eluting with EtOAc/ether (1:1), and the solvent was
removed in vacuo. The vinyl phosphonates were purified
by distillation (Kugelrohr), crystallization or flash
chromatography.
s); 32.20 (Me C, d, J ¼6 Hz); 75.61 (OCH , d, J ¼
2
PC
2
PC
1
6 Hz); 123.78 (vCH–P, d, J ¼182 Hz); 136.39 (vCH ,
PC 2
2
31
21
d, J ¼1.5 Hz). P NMR: 10.8. IR (cm ): 2970, 2910,
PC
1615, 1260.
Acknowledgements
We thank Dr Fr e´ d e´ ric Fotiadu and Jean-Val e` re Naubron for
performing DFT calculations. Financial support from CNRS
as a ‘D e´ l e´ gation’ to M. M. is gratefully acknowledged.
References
1.2.1. 4,4,5,5-Tetramethyl-2-oxo-2-vinyl-1,3,2-dioxa-
phospholane (IIa). Bp 1008C (0.5 Torr). Anal. calcd
1. Minami, T.; Motoyoshiya, J. Synthesis 1992, 333.
2. (a) Raynal, S. Phosphorus Sulfur 1981, 11, 279. (b) Jin, S.;
Gonsalves, K. E. Macromolecules 1998, 31, 1010, and
references cited therein.
1
(
NMR: 1.05 (CH , s); 1.18 (CH , s); 5.53–6.32 (3H, m).
C H O P): C 50.53; H 7.89. Found: C 50.29; H 7.80. H
8 15 3
1
3
C
3
3
3
NMR: 24.06 (CH , d, J ¼5.3 Hz) and 24.72 (CH , d,
3
PC
3
3
1
J ¼3.8 Hz); 88.33 (C–O, s); 126.71 (vC–P, d, J ¼
3. (a) Baldwin, I. C.; Beckett, R. P.; Williams, J. M. J. Synthesis
1996, 34. (b) Cristau, H. J.; Virieux, D. Tetrahedron Lett.
1999, 40, 703. (c) Afarinkia, K.; Binch, H. M.; De Pascale, E.
Synlett 2000, 1769.
PC
PC
2
31
1
2
78.8 Hz); 136.95 (vCH , d, J ¼1.2 Hz). P NMR:
2
PC
6.2. IR (cm2 ): 2995, 1620, 1250, 995.
1
1.2.2. (4S,5S)-Bis(methoxymethyl)-2-oxo-2-vinyl-1,3,2-
dioxaphospholane (IIb). Bp 1308C (0.02 Torr). Anal.
4. (a) Darling, S. D.; Brandes, S. J. J. Org. Chem. 1982, 47, 1413.
(b) Maffei, M.; Buono, G. New J. Chem. 1988, 12, 923.
(c) Maffei, M.; Buono, G. Phosphorus Sulfur 1993, 79, 297.
(d) McClure, C. K.; Hansen, K. B. Tetrahedron Lett. 1996, 37,
2149, and references cited therein. (e) Wyatt, P. B.;
Villalonga-Barber, C.; Motevalli, M. Tetrahedron Lett. 1999,
40, 149, and references cited therein. (f) Robiette, R.; Defacqz,
N.; Stofferis, J.; Marchand-Brynaert, J. Tetrahedron 2003, 59,
4167, and references cited therein.
calcd (C H O P): C 43.24; H 6.76. Found: C 43.65; H
8
15 5
1
7
.00. H NMR: 3.41 (CH , s); 3.43 (CH , s); 3.54–3.73
3 3
(OCH , m); 4.58 (CH–O, t, J ¼2.0 Hz); 5.93–6.56 (3H,
m). C NMR: 59.38 (CH , s); 59.56 (CH , s); 71.84 (OCH ,
3
2
PH
1
3
3 3 2
3
3
d, J ¼5.5 Hz); 72.40 (OCH , d, J ¼4.8 Hz); 78.29
PC
2
PC
2
1
(
1
2
CH–O, d, J ¼19.6 Hz); 124.77 (vCH–P, d, J ¼
PC
PC
21
3
1
79 Hz); 137.77 (vCH , s). P NMR: 30.5. IR (cm ):
2
940, 2900, 1615, 1270, 1050. a (258C)¼219.83 (c¼1.8,
5. (a) Ternansky, R. J.; Pike, A. J. Bioorg. Med. Chem. Lett.
1993, 3, 2237. (b) Breaker, R. R.; Gough, G. R.; Gilham, P. T.
Biochemistry 1993, 32, 9125. (c) Harnden, M. R.; Parkin, A.;
Parratt, M. J.; Perkins, R. M. J. Med. Chem. 1993, 36, 1343.
(d) Rojas-Rousseau, A.; Langlois, N. Tetrahedron 2001, 57,
3389. (e) Engel, R. Chem. Rev. 1977, 77, 349.
D
CH Cl ).
2
2
1.2.3. (4S,5S)-Bis(benzyloxymethyl)-2-oxo-2-vinyl-1,3,2-
dioxaphospholane (IIc). Yellowish oil (R : 0.45 ether/ethyl
f
acetate 1.5:1). Anal. calcd (C H O P): C 64.17; H 6.15.
20 23 5