Highly enantioselective preparation of fluorinated phosphonates by michael addition of α-fluoro-β-ketophosphonates to nitroalkenes

Abstract

Fluorinated phosphonates are excellent surrogates of phosphates, outperforming the latter in terms of hydrolytic stability in biological systems while retaining similar activities. However, methods for preparing chiral fluorinated phosphonates are very limited. In this report, racemic α-fluoro-β-ketophosphonates were used in stereoselective Michael addition to nitroalkenes promoted by trifunctional thiourea organocatalyst. Highly functionalised α-fluoro-β-keto-γ-nitrophosphonates were obtained in high yields of 84-99% with excellent stereochemical control (96-99% ee and 3:1-34:1 d.r.). © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.