Mechanism and Stereoselectivity of the Phosphinylation of 3-Acyl Coumarins-Stereocontrol Via Concurrent Aromatic Interaction/Oxaphosphole Formation

Petar   Y.   Petrov; Nikolay   G.   Vassilev; Silvia   E.   Angelova; Boris   L.   Shivachev; Galin   P.   Petrov

doi:10.2174/157017809787582825

Abstract

Racemic P-acetoxy-P-chloro phenylphosphonite reacts with prochiral 3-acylcoumarins yielding (2R,3R)/(2S,3S)-coumarino-3,4-c-2-oxo-2-phenyl-1,2-3H-oxaphospholes with > 99% regio- and diastereoselectivity. The stereoselectivity is governed by the presence of phophonite phenyl group and oxaphosphole ring formation. The product has suitable conformation providing stereoselective route to (R,S)/(S,R) phosphino-substituted coumarins, normally inaccessible by the Phospha-Michael reaction employing achiral reagents.

Keywords: Phosphonylation, phosphinylation, diastereoselectivity, dynamic NMR, kinetics, oxaphospholes

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Letters in Organic Chemistry

Title: Mechanism and Stereoselectivity of the Phosphinylation of 3-Acyl Coumarins-Stereocontrol Via Concurrent Aromatic Interaction/Oxaphosphole Formation

Volume: 6 Issue: 2

Author(s): Petar Y. Petrov, Nikolay G. Vassilev, Silvia E. Angelova, Boris L. Shivachev and Galin P. Petrov

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Keywords: Phosphonylation, phosphinylation, diastereoselectivity, dynamic NMR, kinetics, oxaphospholes

Abstract: Racemic P-acetoxy-P-chloro phenylphosphonite reacts with prochiral 3-acylcoumarins yielding (2R,3R)/(2S,3S)-coumarino-3,4-c-2-oxo-2-phenyl-1,2-3H-oxaphospholes with > 99% regio- and diastereoselectivity. The stereoselectivity is governed by the presence of phophonite phenyl group and oxaphosphole ring formation. The product has suitable conformation providing stereoselective route to (R,S)/(S,R) phosphino-substituted coumarins, normally inaccessible by the Phospha-Michael reaction employing achiral reagents.

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Petrov Y. Petar, Vassilev G. Nikolay, Angelova E. Silvia, Shivachev L. Boris and Petrov P. Galin, Mechanism and Stereoselectivity of the Phosphinylation of 3-Acyl Coumarins-Stereocontrol Via Concurrent Aromatic Interaction/Oxaphosphole Formation, Letters in Organic Chemistry 2009; 6 (2) . https://dx.doi.org/10.2174/157017809787582825