1452
B. Kaboudin, F. Saadati / Tetrahedron Letters 50 (2009) 1450–1452
10. (a) Schmidt, H. Chem. Ber. 1948, 81, 477–483; (b) Linfield, W. M.; Jungermann,
E.; Guttmann, A. T. J. Org. Chem. 1961, 26, 4088–4092; (c) Yamagishi, T.; Haruki,
T.; Yokomatsu, T. Tetrahedron 2006, 62, 9210–9217; (d) Cates, L. A.; Li, V. S.
Pharm. Res. 1985, 136; (e) Lecoq, A.; Yiotakis, A.; Dive, V. Synth. Commun. 1994,
24, 2877–2892; (f) Hamilton, R.; Walker, B.; Walker, B. J. Tetrahedron Lett. 1995,
36, 4451–4454; (g) Kaboudin, B.; As-Habei, N. Tetrahedron Lett. 2003, 44, 4243–
4245; (h) Pirat, J.-L.; Monbrun, J.; Virieux, D.; Volle, J.-N.; Tillard, M.; Cristau,
H.-J. J. Org. Chem. 2005, 70, 7035–7041; (i) Boyd, E. A.; Chan, W. C.; Loh, V. M., Jr.
Tetrahedron Lett. 1996, 37, 1647–1650.
11. Jiao, X.-Y.; Verbruggen, C.; Borloo, M.; Bollaert, W.; Groot, A. D.; Dommisse, R.;
Haemers, A. Synthesis 1994, 23–24.
12. (a) Lewkowski, J. J. Organomet. Chem. 2003, 681, 225–227; (b) Lewkowski, J.
Heteroat. Chem. 2004, 15, 162–168.
13. Tyka, R.; Hagele, G. Phosphorus, Sulfur, Silicon 1989, 44, 103–107.
14. (a) Saigo, K.; Kubota, N.; Takebayashi, S.; Hasegawa, M. Bull. Chem. Soc. Jpn.
1986, 59, 931–932; (b) Corey, E. J.; Kuhnle, F. N. M. Tetrahedron Lett. 1997, 38,
8631–8634; (c) Larter, M. L.; Phillips, M.; Ortega, F.; Aguirre, G.; Somanathan,
R.; Walsh, P. J. Tetrahedron Lett. 1998, 39, 4785–4788; (d) Lozinskaya, N. A.;
Tsybezova, V. V.; Proskurnina, M. V.; Zefirov, N. S. Russ. Chem. Bull. 2003, 52,
674–678; (e) Nishiyama, K.; Saito, M.; Oba, M. Bull. Chem. Soc. Jpn. 1988, 61,
609–611; (f) Uchida, H.; Shimizu, T.; Reddy, P. Y.; Nakamura, S.; Toru, T.
Synthesis 2003, 1236–1240; (g) Uchida, H.; Tanikoshi, H.; Nakamura, S.; Reddy,
P. Y.; Toru, T. Synlett 2003, 1117–1120; (h) Kaboudin, B.; Saadati, F. Heterocycles
2005, 65, 353–357.
15. (a) Corey, E. J.; Grogan, M. J. Org. Lett. 1999, 1, 157–160; (b) Isobe, T.; Fukuda,
K.; Araki, Y.; Ishikawa, T. Chem. Commun. 2001, 243–244; (c) Anastassiadou,
M.; Baziard-Mouysset, G.; Payard, M. Synthesis 2000, 1814–1816; (d) Corey, E.
J.; Huang, H. C. Tetrahedron Lett. 1989, 30, 5235; (e) Corey, E. J.; Imwinkelried,
R.; Pikul, S. B. J. Am. Chem. Soc. 1989, 111, 5493–5495; (f) Corey, E. J.; Kim, S. S. J.
Am. Chem. Soc. 1990, 112, 4976–4977.
62.1 (m, CHP), 127.0, 127.5, 127.7, 128.5, 128.7, 128.9, 134.9, 136.5; 31P NMR
(D2O/H3PO4-101.2 MHz): 17.58, 17.85 (40:60) ppm; IR (KBr): 3650–2120 (–
OH), 1250 (P@O), 1055–710 (P–O) cmꢀ1; Anal. Calcd for C14H17NO4P2: C, 51.68;
H, 5.27; N, 4.31. Found: C, 51.55; H, 5.20; N, 4.56. Compound 2b: white solid,
single diastereoisomer, mp: 240–242 °C; 1H NMR (D2O/TMS-250 MHz): 3.79
(2H, d, J = 14.0 Hz, –CHP), 6.84 (2H, d, JHP = 552 Hz), 6.91 (4H, d, J = 7.2 Hz), 7.21
(4H, d, J = 7.2 Hz); 13C NMR (D2O–NaOD/TMS-62.9 MHz): 59.2–61.5 (m, CHP),
128.7, 130.1 (d, JCP = 5.7 Hz), 132.8 (d, JCP = 3.1 Hz), 133.4 (d, JCP = 3.8 Hz); 31P
NMR (D2O/H3PO4-101.2 MHz): 17.37 ppm; IR (KBr): 3650–2120 (–OH), 1250
(P@O), 1080–750 (P–O) cmꢀ1; Anal. Calcd for C14H15Cl2NO4P2. C, 42.75; H,
3.85; N, 3.56. Found: C, 42.56; H, 3.80; N, 3.52. Compound 2c: white solid,
single diastereoisomer, mp: 230–232 °C; 1H NMR (D2O/TMS-250 MHz): 3.98
(2H, d, J = 13.5 Hz, –CHP), 6.99 (2H, d, JHP = 552 Hz), 7.01–7.15 (m, 8H); 31P
NMR (D2O/H3PO4-101.2 MHz): 17.22 ppm; IR (KBr): 3650–2120 (ꢀOH), 1240
(P@O), 1180–580 (P–O) cmꢀ1 13C NMR (D2O-NaOD/TMS-62.9 MHz): 60.1 (dd,
;
JCP = 98.5 and 14.1 Hz), 115.4 (d, JCP=21.4 Hz), 130.1–130.5 (m, Ar), 162.1 (d,
JCP = 243.2 Hz), Anal. Calcd for C14H15F2NO4P2: C, 46.53; H, 4.19; N, 3.88.
Found: C, 46.56; H, 4.12; N, 3.72. Compound 2d: white solid, single
diastereoisomer, mp: 212–214 °C; 1H NMR (D2O/TMS-250 MHz): 3.63 (s, 6H),
3.73 (2H, d, J = 14.5 Hz, –CHP), 6.86 (2H, d, JHP = 550 Hz), 6.82 (4H, d, J = 8.0 Hz),
6.90 (4H, d, J = 8.0 Hz); 31P NMR (D2O/H3PO4-101.2 MHz): 17.81 ppm; IR (KBr):
3650–2320 (ꢀOH), 1248 (P@O), 1150–650 (P–O) cmꢀ1
;
13C NMR (D2O–NaOD/
TMS-62.9 MHz): 55.3, 59.2–61.5 (m, CHP), 114.8, 120.4, 130.1 (d, JCP = 5.5 Hz),
159.7; Anal. Calcd for C16H21NO6P2: C, 49.86; H, 5.50; N, 3.64. Found: C, 49.71;
H, 5.43; N, 3.52. Compound 2e: white solid, mixture of two diastereoisomers;
1H NMR (D2O/TMS-250 MHz): 2.07, 2.10 (s, 6H), 3.72, 4.12 (2H, 2d, J = 14.0 Hz,
ꢀCHP), 6.83, 6.88 (2H, 2d, JHP = 551 Hz), 6.75–7.17 (8H, m); 31P NMR (D2O/
H3PO4-101.2 MHz): 17.86, 18.12 ppm; IR (KBr): 3650–2220 (ꢀOH), 1251
(P@O), 1185–610 (P–O) cmꢀ1 13C NMR (D2O–NaOD/TMS-62.9 MHz): 20.1,
;
60.0–62.1 (m, CHP), 128.4 (d, JCP = 5.7 Hz), 128.8 (d, JCP = 5.7 Hz), 129.0, 129.2,
131.6, 133.3, 137.6 (d, JCP = 3.1 Hz), 137.9 (d, JCP = 3.1 Hz). Anal. Calcd for
C16H21NO4P2: C, 54.38; H, 5.99; N, 3.96. Found: C, 54.30; H, 5.85; N, 4.05.
Compound 2f: white solid, single diastereoisomer, mp: 226–228 °C; 1H NMR
(D2O/TMS-250 MHz): 4.15 (2H, d, J = 14.7 Hz, ꢀCHP), 6.90 (2H, d,
JHP = 557.5 Hz), 6.75–7.85 (m, 8H); 31P NMR (D2O/H3PO4-101.2 MHz):
16. (a) Kaboudin, B.; Moradi, K. Synthesis 2006, 2339–2342; (b) Kaboudin, B.; Jafari,
E. Synthesis 2006, 3063–3066.
17. (a) Kaboudin, B. Chem. Lett. 2001, 880–881; (b) Kaboudin, B.; Nazari, R.
Tetrahedron Lett. 2001, 42, 8211; (c) Kaboudin, B.; Nazari, R. Synth. Commun.
2001, 31, 2245–2250; (d) Kaboudin, B. Tetrahedron Lett. 2002, 43, 8713–8714;
(e) Kaboudin, B. Tetrahedron Lett. 2003, 44, 1051–1053; (f) Kaboudin, B.;
Rahmani, A. Synthesis 2003, 2705–2708; (g) Kaboudin, B.; Saadati, F. Synthesis
2004, 1249–1252; (h) Kaboudin, B.; Rahmani, A. Org. Prep. Proced. Int 2004, 36,
82–86; (i) Kaboudin, B.; Moradi, K. Tetrahedron Lett. 2005, 46, 2989–2991; (j)
Kaboudin, B.; Haghighat, H. Tetrahedron Lett. 2005, 46, 7955–7957; (k)
Kaboudin, B.; Haghighat, H.; Yokomatsu, T. J. Org. Chem. 2006, 71, 6604–
6606; (l) Kaboudin, B.; Karimi, M. Bioorg. Med. Chem. Lett. 2006, 16, 5324–5327;
(m) Kaboudin, B.; Farjadian, F. Beilstein J. Org. Chem 2006, 2, 4; (n) Yamagishi,
T.; Kusano, T.; Kaboudin, B.; Yokomatsu, T.; Sakuma, C.; Shibuya, S. Tetrahedron
2003, 59, 767–772; (o) Kaboudin, B.; Haruki, T.; Yamaghishi, T.; Yokomatsu, T.
Tetrahedron 2007, 63, 8199–8205; (p) Kaboudin, B.; Haruki, T.; Yamagishi, T.;
Yokomatsu, T. Synthesis 2007, 3226–3232; (q) Kaboudin, B.; Haghighat, H.;
Yokomatsu, T. Tetrahedron: Asymmetry 2008, 19, 862–866.
15.95 ppm; IR (KBr): 3650–2120 (ꢀOH), 1240 (P@O), 1180–580 (P–O) cmꢀ1
;
13C NMR (D2O–NaOD/TMS-62.9 MHz): 60.1 (dd, JCP = 98.5 and 14.1 Hz), 116.1
(d, JCP = 21.4 Hz), 125.3–130.5 (m, Ar), 161.1 (d, JCP = 242.0 Hz), Anal. Calcd for
C14H15F2NO4P2: C, 46.53; H, 4.19; N, 3.88. Found: C, 46.50; H, 4.15; N, 3.75.
Compound 2g: white solid, single diastereoisomer, mp: 212–214 °C; 1H NMR
(D2O/TMS-250 MHz): 4.13 (2H, d, J = 13.2 Hz, –CHP), 7.13 (2H, d, JHP = 551 Hz),
6.90–7.80 (m, 12H), 6.90 (2H, d, J = 8.0 Hz); 31P NMR (D2O/H3PO4-101.2 MHz):
17.80 ppm; IR (KBr): 3650–2100 (ꢀOH), 1248 (P@O), 1050–750 (P–O) cmꢀ1
;
13C NMR (D2O–NaOD/TMS-62.9 MHz): 61.2 (dd, JCP = 97.5 and 13.8 Hz), 126.1–
126.5 (m, Ar) 127.6, 128.0 (d, JCP = 7.0 Hz), 128.2, 132.5, 132.6 132.9; Anal.
Calcd for C22H21NO4P2: C, 62.10; H, 4.98; N, 3.29. Found: C, 61.97; H, 5.03; N,
3.22.
20.
A mixture of phosphinic acid 2a (one diastereoisomer, 1 mmol) and
18. Matziari, M.; Georgiadis, D.; Dive, V.; Yiotakis, A. Org. Lett. 2001, 3, 659–662.
19. The aldehyde (3 mmol) was added to ammonium hydroxide (30%, 15 mL), and
the solution was stirred for 5 h at reflux. During this time, a white precipitate
formed. The precipitate was removed by filtration and dried. The solid was
dissolved in 5 mL of ethanol, and anhydrous hypophosphorus acid (5 mmol)
was added to this mixture and the resulting solution was stirred for 2–12 h at
reflux. The solvent was evaporated and the mixture was dissolved in acetone
by heating. Dropwise addition of water gave the crude product as a white solid.
The crude product was washed with ethanol and dried in air at room
temperature to give product 2 in 40–71% yield. The solid product was washed
with ethanol/water (50 ml, 9:1) and dried in air at room temperature to give a
single diastereoisomer. All products gave satisfactory spectral data in accord
with the assigned structures. Analytical and spectral data for compounds 2:
Compound 2a: white solid, mixture of two diastereoisomers; 1H NMR (D2O/
TMS-250 MHz): 3.79, 4.16 (2H, 2d, J = 13.5 Hz, –CHP), 6.83, 6.88 (2H, 2d,
JHP = 552 Hz), 6.85–7.40 (10H, m); 13C NMR (D2O-NaOD/TMS-62.9 MHz): 60.0–
1,1,1,3,3,3-hexamethyldisilazane (5 mmol, 1 mL) was heated at 110 °C for
2 h under Ar. The mixture was cooled to rt. Methyl acrylate (2 mmol,
0.18 mL) was added dropwise and the resulting mixture was stirred at 60 °C
for 12 h. Absolute EtOH (10 mL) was added and the mixture was cooled to rt
slowly. The solvent was removed under vacuum. The residue was treated
with a solution of sodium bicarbonate (5%, 10 mL) and extracted with ethyl
acetate (3 ꢁ 10 mL). The aqueous solution was acidified with HCl (5%), and
extracted with CHCl3 (4 ꢁ 10 mL). The combined organic layers were washed
with brine, dried over Na2SO4 and evaporated under reduced pressure to
give 3a as a white solid in 85% yield. Mp: 95–96 °C; 1H NMR (DMSO/TMS-
250 MHz): 1.55–1.90 (m, 4H), 2.20–2.40 (m, 4H), 3.54 (s, 8H), 5.10–5.75 (br
s, NH), 7.10–7.40 (m, 10H); 31P NMR (DMSO/H3PO4-101.2 MHz): 43.68 ppm;
13C NMR (DMSO/TMS-62.9 MHz): 21.8 (d, JCP = 93.7 Hz), 26.6, 52.0, 59.9 (dd,
JCP = 99.8 and 13.3 Hz), 127.2–129.5 (m, Ar), 135.6, 172.9 (d, JCP = 16.1 Hz);
Anal. Calcd for C22H29NO8P2: C, 53.10; H, 5.89; N, 2.82. Found: C, 53.05; H,
5.80; N, 2.65.