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DOI: 10.1055/s-2005-871553
Rhodium Acetate-Mediated Epoxidation from the Reaction of Diazobenzylphosphonates with Aldehydes and a Ketone: A Convenient and Highly Stereoselective Synthetic Method of cis-1,2-Epoxypropylphosphonates
Publication History
Publication Date:
28 June 2005 (online)
Abstract
The first stereoselective synthetic route to 1,2-epoxyalkylphosphonates from the reaction of dimethyl diazophosphonate with aldehydes or a ketone using a dirhodium complex as catalyst is reported. The experimental results showed that only a single isomer of the epoxide product was obtained from the catalytic reaction, which gave (1R * ,2S * )-(Z)-1,2-epoxyalkylphosphonate in good yield and completely chemoselectively without the formation of the 1,3-dipolar cycloaddition product 1,3-dioxolane.
Key words
1,2-epoxyalkylphosphonates - rhodium acetate - epoxidation - stereoselectivity
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Hendlin D.Stapley EO.Jackson M.Wallick H.Miller AK.Wolf FJ.Miller TW.Chaier L.Kahan FM.Foltz EL.Woodruff HB.Mata JM.Hernandez S.Mochales S. Science (Washington, D.C.) 1969, 166: 122 - 2
Christensen BG.Leanza WJ.Beattie TR.Patchett AA.Arison BH.Ormond RE.Kuehl FA.Albers-Schonberg G.Jardetzky O. Science (Washington, D. C.) 1969, 166: 123 -
3a
Iorga B.Eymery F.Savignac P. Synthesis 1999, 207 ; and the references cited therein -
3b
Fields SC. Tetrahedron 1999, 55: 12237 - 4
Begum S.Rahman MM.Takagi R.Ohkata K. Heterocycles 2004, 62: 251 - 5
Doyle MP.McKervey MA.Ye T. Modern Catalytic Methods for Organic Synthesis with Diazo Compounds Chap. 7: John Wiley and Sons; New York: 1998. p.397 - 6
Padwa A.Hornbuckle S. Chem. Rev. 1991, 91: 263 -
7a
Padwa A.Weingarten MD. Chem. Rev. 1996, 96: 223 -
7b
Doyle MP.Forbes DC. Chem. Rev. 1998, 98: 911 -
7c
Hodgson DM.Pierard FYTM.Stupple PA. Chem. Soc. Rev. 2001, 30: 50 -
7d
Mehta G.Muthusamy S. Tetrahedron 2002, 58: 9477 - 8
Huisgen R.De March P. J. Am. Chem. Soc. 1982, 104: 4955 - 9
Doyle MP.Forbes DC.Protopopova MN.Stanley SA.Vasbinder MM.Xavier KR. J. Org. Chem. 1997, 62: 7210 - 10
Doyle MP.Hu WH.Timmons DJ. Org. Lett. 2001, 3: 933 - 11
Davies HML.DeMeese J. Tetrahedron Lett. 2001, 42: 6803 - 12
Muthusamy S.Gunanathan C.Nethaji M. Synlett 2004, 639 - 13
Seyferth D.Marmon RS.Hilbert P. J. Org. Chem. 1971, 36: 1379 - 14
Afarinkia K.Cadogan JG.Rees CW. Chem. Commun. 1992, 285 - 15
Paul-Roth C.De Montigny F.Rethore G.Simonneaux G.Gulea M.Masson S. J. Mol. Catal. A: Chem. 2003, 201: 79 - 16
Joergensen KA. Chem. Rev. 1989, 89: 431 - 17
Aggarwal VK.Winn CL. Acc. Chem. Res. 2004, 37: 611 - 20
Lu CD.Chen ZY.Liu H.Hu WH.Mi AQ. Org. Lett. 2004, 6: 3071 - 21
Lu CD.Chen ZY.Liu H.Hu WH.Mi AQ.Doyle MP. J. Org. Chem. 2004, 69: 4856
References
Selected bond lengths [Å] and bond angles [°]: P-O6: 1.457 (6), P-O4: 1.565 (6), P-O5: 1.5681 (15), P-C7: 1.820 (2), O1-C8: 1.430 (3), O1-C7: 1.448 (2), C7-C8: 1.485 (3), C6-C7: 1.500(3), C8-C9: 1.495 (3), C8-H8: 0.980; C8-O1-C7: 62.10 (13), O1-C7-C8: 58.38 (13), O1-C8-C7: 59.52 (13), O1-C7-P: 114.34 (14), O1-C8-H8: 114.30.
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Typical procedure for the epoxidation of arylaldehydes or ketones with dimethyl diazophosphonate.
A solution of aldehyde or ketone (2.4 mmol), catalyst (0.09 mmol), and diazophosphonate (2.2 mmol) in toluene (10 mL) was heated to reflux under an argon atmosphere. The reaction was monitored by TLC. After the reaction was complete, the mixture was cooled to room temperature and the solvent was removed in vacuo, and a portion of the crude product was subjected to 1H NMR analysis to determine the isomer ratio. The crude product was purified by column chromatography on silica gel using petroleum ether-EtOAc, 3:1 as eluent to give epoxides.
Detailed spectral data of product 3, and the crystal data for compound 3f, are available upon request from the author.