Synthesis of Chiral α-(N-Sulfoximido) Phosphines, Phosphine Oxides, and Phosphonates through Hydrophosphination and Hydrophosphorylation of N-Vinyl Sulfoximines

Abstract

The reaction of N-vinyl sulfoximines with HPPh₂, HP(O)Ph₂, and HP(O)(OMe)₂ gave the corresponding α-(N-sulfoximido) phosphines, phosphine oxides, and phosphonates, respectively, with high regioselectivity in high yield. The N-vinyl sulfoximines showed an enamine-like regioselectivity in hydrophosphination and hydrophosphorylation (Pudovik reaction). While the acid-catalyzed hydrolysis of a cyclic N-vinyl sulfoximine gave the corresponding NH-sulfoximine and cyclohexanone, its hydro­boration/oxidation afforded the corresponding N-(β-hydroxycyclohexenyl) sulfoximine. The structure of an α-(N-sulfoximido) phosphine was determined by X-ray crystal structure analysis.

Key words

Pudovik reaction - N-vinyl sulfoximines - hydrophos­phination - hydrophosphorylation - phosphines - α-(N-sulfoximido) phosphines - α-(N-sulfoximido) phosphine oxides - α-(N-sulfoximido) phosphonates - hydroboration

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Crystallographic data have been deposited with the Cambridge Crystallographic Data Centre as supplementary publication no. CCDC 662748. 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 www.ccdc.cam.ac.uk].