Camphor-based oxazaphospholanes as chiral templates for the enantioselective synthesis of α-chlorophosphonic acids

(a) The Role of Phosphonates in Living Systems; Hilderbrand, R. L., Ed.; CRC Press: Boca Raton, FL, 1983; (b) Engel, R. Chem. Rev. 1977, 77, 349–367; (c) Kukhar', V. P.; Solodenko, V. A. Russ. Chem. Rev. 1987, 56, 859–874. McKenna, C. E.; Khawli, L. A.; Bapat, A.; Harutunian, V.; Cheng, Y.-C. Biochem. Pharmacol. 1987, 36, 3103–3106. Kametani, T.; Kigasawa, K.; Hiiragi, M.; Wakisaka, K.; Haga, S.; Sugi, H.; Tanigawa, K.; Suzuki, Y.; Fukawa, K.; Irino, O.; Saita, O.; Yamabe, S. Heterocycles 1981, 16, 1205–1242. (a) Hanessian, S.; Bennani, Y. L.; Delorme, D. Tetrahedron Lett. 1990, 31, 6461–6464; (b) Jacquier, R.; Lhassani, M.; Petrus, C.; Petrus, F. Phosphorus and Sulfur 1993, 81, 83–87; (c) Yuan, C. Y.; Li, S. S.; Wang, G. Q.; Wu, H. Chin. Chem. Lett. 1993, 4, 753–756. (a) Colombo, L.; DiGiacomo, M.; Brusotti, G.; Milano, E. Tetrahedron Lett. 1995, 36, 2863–2866; (b) Denmark, S. E.; Rivera, I. J. Org. Chem. 1994, 59, 6887–6889; (c) Bonner, M. P.; Thornton, E. R. J. Am. Chem. Soc. 1991, 113, 1299–1308; (d) Kouklovsky, C.; Pouilhes, A.; Langlois, Y. J. Am. Chem. Soc. 1990, 112, 6672–6679; (e) Oppolzer, W. Tetrahedron 1987, 43, 1969–2004. Selected data. Compound 3: m.p. 115°C (hexane–Et2O); [α]D25=−29.5 (c 1, CHCl3); 1H NMR (CDCl3, 200 MHz) δ 4.37 dd [1H] (3J=7.6 Hz, 3JH–P=5.2 Hz), 3.89 dd [1H] (2JAB=14.5 Hz, 2JH–P=11.8 Hz), 3.70 dd [1H] (2JAB=14.5 Hz, 2JH–P=6.4 Hz), 3.59 dd [1H] (3J=7.6 Hz, 3JH–P=4.9 Hz), 3.55 m [1H], 2.02 d [1H] (3J=4.5 Hz), 1.85–1.45 m [3H], 1.40 d [3H] (3J=6.5 Hz), 1.36 d [3H] (3J=6.5 Hz), 1.34 s [3H], 1.05 s [3H], 0.97 m [1H], 0.88 s [3H]; 31P NMR (CDCl3, 81.0 M Hz) δ 35.99; Elem. anal.: C, 54.85; H, 8.20; N, 4.50; calcd for C14H25ClNO2P: C, 54.99; H, 8.24; N, 4.58. Compound 5d: m.p. 108°C (hexane–Et2O); [α]D25=+8.45 (c 1.6, CHCl3); 1H NMR (CDCl3) δ 7.32 m [5H], 4.39 dd [1H] (3J=7.5 Hz, 3JH–P=5.3 Hz), 4.23 ddd [1H] (2JH–P=11.9 Hz, 3J=6.2 Hz, 3J=2.4 Hz), 3.74 ddd [1H] (2JAB=14.7 Hz, 3JH–P=5.3 Hz, 3J=2.4 Hz), 3.57 dd [1H] (3J=7.5 Hz, 3JH–P=4.6 Hz), 3.56 m [1H], 3.05 ddd [1H] (2JAB=14.7 Hz, 3JH–P=5.7 Hz, 3J=11.9 Hz), 2.04 d [1H] (3J=5.0 Hz), 1.77–1.55 m [3H], 1.39 d [3H] (3J=6.7 Hz), 1.37 s [3H], 1.34 d [3H] (3J=6.6 Hz), 1.08 s [3H], 0.97 m [1H], 0.90 s [3H]; 31P NMR (CDCl3) δ 38.18; Elem. anal.: C, 63.65; H, 7.97; N, 3.50; calcd for C21H31ClNO2P: C, 63.71; H, 7.89; N, 3.54. Jommi, G.; Miglierini, G.; Pagliarin, R.; Sello, G.; Sisti, M. Tetrahedron 1992, 35, 7275–7288. Johnson, C. K. ORTEP II, 1976 Report ORNL-5138. Oak Ridge National Laboratory, Tenn., USA. The chiral auxiliary was recovered almost quantitatively with unchanged enantiomeric excess. Fait, J. XSCANS User Manual, 1991. Siemens Analytical X-Ray Instruments, Inc., Madison, Wisconsin, USA. Altomare, A.; Cascarano, G.; Giacovazzo, G.; Guagliardi, A.; Burla, M. C.; Polidori G.; Camalli, M. J. Appl. Cryst. 1994, 27, 435. Sheldrick, G. M. SHELX97. Program for the Refinement of Crystal Structures, 1997. Univ. of Göttingen, Germany. Flack, H. D. Acta Cryst. 1983, A39, 876–881.