Asymmetric Michael Additions of a Chiral Phosphite to Nitroalkenes and Knoevenagel Acceptors

Abstract

The diastereoselective Michael addition of an enantiopure phosphite to nitroalkenes and α,β-unsaturated malonates is described. High asymmetric inductions were obtained using a readily available TADDOL auxiliary. Racemization-free cleavage of the auxiliary led to α-substituted β-nitro phosphonates and β-substituted β-phosphono malonates in good yields and high enantiomeric excesses, respectively. An extension of the method to the synthesis of α,β-disubstituted β-nitrophosphonates with two new neighboring stereogenic centers is also reported.

Key Words

Michael addition - nitroalkenes - phosphonates - P-C bond formation - asymmetric synthesis

References

• 1a Horiguchi M. Biochim. Biophys. Acta  1972,  261:  102 
• 1b Hildebrand RL. The Role of Phosphonates in Living Systems   Hildebrand RL. CRC Press; Boca Raton: 1983. 
• 2a Christiansen BG. Leanza WJ. Beattie TR. Patchett A. Arison BH. Ormond RE. Kuehl FA. Albers-Schonberg G. Jardetzky O. Science  1969,  166:  123 
• 2b Glamowski EJ. Gal G. Purick R. Davidson AJ. Sletzinger M. J. Org. Chem.  1970,  35:  3510 
• 2c Giordano C. Castaldi G. J. Org. Chem.  1989,  54:  1470 
• 2d Allen JG. Atherton FR. Hall MJ. Hassal CH. Holmes SW. Lambert RW. Nisbet LJ. Ringrose PS. Nature  1978,  272:  56 
• 3a Duke S. Lydon J. Weed Technol.  1987,  1:  122 
• 3b Leason M. Cunliffe D. Parklin D. Lea PJ. Miflin BJ. Phytochemistry  1982,  21:  855 
• 3c Diddens H. Zähner H. Kraas E. Göhring W. Jung WG. Eur. J. Biochem.  1976,  66:  11 
• 4 Kido Y. Hamakado T. Anno M. Miyagawa E. Motoki Y. J. Antibiot.  1984,  37:  965 
• 5a Van Herrewege Y. Penne L. Vereecken C. Fransen K. Van Der Groen G. Kestens L. Balzarini J. Vanham G. Aids Res. Human Retroviruses  2002,  18:  1091 
• 5b Guan H.-P. Qiu Y.-L. Ksebati MB. Kern ER. Zemlicka J. Tetrahedron  2002,  58:  6047 
• 5c Aquaro S. Calio R. Balzarini J. Bellocchi MC. Garaci E. Perno CF. Antiviral Res.  2002,  55:  209 
• 6a Michaelis A. Kaehne R. Ber. Dtsch. Chem. Ges.  1898,  31:  1048 
• 6b Arbusov BA. Pure Appl. Chem.  1964,  9:  307 
• 6c Kosolapoff GM. Org. React. (N. Y.)  1951,  6:  273 
• 6d Pommer H. Angew. Chem.  1960,  72:  811 
• 7a Pudovik AN. Arbuzov BA. Dokl. Akad. Nauk SSSR  1950,  73:  327 
• 7b Pudovik AN. Dokl. Akad. Nauk SSSR  1950,  73:  499 
• 7c Pudovik AN. Arbuzov BA. Zh. Obshch. Khim.  1951,  21:  382 
• 7d Pudovik AN. Arbuzov BA. Zh. Obshch. Khim.  1951,  21:  423 
• 7e Pudovik AN. Arbuzov BA. Zh. Obshch. Khim.  1951,  21:  1837 
• 7f Pudovik AN. Arbuzov BA. Zh. Obshch. Khim.  1952,  22:  462 
• 8 For a review, see: Pudovik AN. Konovalova IV. Synthesis  1979,  793 
• 9a Tollefson MB. Li JJ. Beak P. J. Am. Chem. Soc.  1996,  118:  9052 
• 9b Jugé S. Waksleman M. Genêt JP. Tetrahedron Lett.  1990,  31:  4442 
• 9c Jugé S. Genêt JP. Tetrahedron Lett.  1989,  30:  2783 
• For recent reviews on asymmetric Michael additions, see:
• 10a Xu L.-W. Xia C.-G. Eur. J. Org. Chem.  2005,  633 
• 10b Berner OM. Tedeschi L. Enders D. Eur. J. Org. Chem.  2002,  1877 
• 10c Alexakis A. Benhaim C. Eur. J. Org. Chem.  2002,  3221 
• 10d Krause N. Hoffmann-Röder A. Synthesis  2001,  171 
• 10e Sibi MP. Manyem S. Tetrahedron  2000,  56:  8033 
• 10f Leonard J. Diez-Barra E. Merino S. Eur. J. Org. Chem.  1998,  2051 
• 10g Yamamoto Y. Pyne SG. Schinzer D. Feringa BL. Jansen JFGA. In Houben Weyl - Methoden der Organischen Chemie   4th ed., Vol. E21b:  Helmchen G. Hoffmann RW. Mulzer J. Schaumann E. Thieme; Stuttgart: 1995.  Chap. 1.5.2.
• 10h Rossiter BE. Swingle NM. Chem. Rev.  1992,  92:  771 For a review on phospha-Michael additions see:
• 10i Enders D. Saint-Dizier A. Lannou M.-I. Lenzen A. Eur. J. Org. Chem.  2006,  29 
• 11 Enders D. Tedeschi L. Bats JW. Angew. Chem. Int. Ed.  2000,  39:  4605 ; Angew. Chem. 2000, 112, 4774
• 12 Tedeschi L. Enders D. Org. Lett.  2001,  3:  3515 
• 13 For the application of 1 in nucleophilic acylations of unsaturated amides, see: Nahm MR. Linghu X. Potnick JR. Yates CM. White PS. Johnson JS. Angew. Chem. Int. Ed.  2005,  44:  2377 ; Angew. Chem. 2005, 117, 2429
• 14a Beck AK. Bastani B. Plattner DA. Petter W. Seebach D. Braunschweig H. Gysi P. La Vecchia L. Chimia  1991,  45:  238 
• 14b Seebach D. Beck AK. Heckel A. Angew. Chem. Int. Ed.  2001,  40:  92 ; Angew. Chem. 2001, 113, 96
• 15a Noltes JG. Recl. Trav. Chim. Pays-Bas  1965,  84:  782 
• 15b Boersma J. Noltes JG. Recl. Trav. Chim. Pays-Bas  1973,  92:  229 
• 16 Patel VD. Schmidt RJ. Biller SA. Gordon EM. Robinson SS. Manne V. J. Med. Chem.  1995,  38:  2906 
• 17a Semenzin D. Etemad-Moghadam G. Albouy D. Diallo O. Koenig M. J. Org. Chem.  1997,  62:  2414 
• 17b Albouy D. Laspéras M. Etemad-Moghadam G. Koenig M. Tetrahedron Lett.  1999,  40:  2311 

18

The crystal structure of 8e has been deposited as supplementary publication no. CCDC-281444 at the Cambridge Crystallographic Data Centre. Copies of the data can be obtained free of charge on application to CCDC 12 Union Road Cambridge CB2 1EZ UK [fax: [phone]; e-mail: [e-mail] or
http//www.ccdc.cam.ac.uk].