Synthesis of β-keto Phosphonates From Vinyl Phosphates Via a 1,3-phosphorus Migration

Abstract

A new method for the preparation of β-keto phosphonates has been developed, involving rearrangement of vinyl phosphates upon treatment with strong base. Because this approach ultimately relies upon electrophilic dialkyl phosphorochloridates as the phosphorus source, it is complementary to such traditional methods for 0-keto phosphonate synthesis as the Arbuzov reaction or the acylation of alkyl phosphonate anions. This new method provides ready access to β-keto phosphonates derived from cyclic ketones, compounds that historically have been very inaccessible. © 1987, American Chemical Society. All rights reserved.