James J. Napier

A process for the synthesis of β-ketoesters using in-situ generated (trimethylsilyl)malonates

Abstract (TMS)ethyl malonate can be generated in-situ by treating potassium ethyl malonate with trimethylsilyl chloride and acylated with aliphatic or aromatic acyl imidazoles or chlorides in the presence of DBU to prepare a variety of β-ketoesters. This constitutes a high yield method for preparing β-ketoesters, which also can be extended to the formation of alkylidene malonates.

Rearrangement of a 2-aryloxycyclohex-2-enone. A new enolate Claisen rearrangement?

The base-catalysed rearrangement of the 2-aryl-oxycyclohex-2-enone (3) to the enone (4a) is suggested to occur by an enolate-promoted 3,3-sigmatropic rearrangement of the enolate aryl ether (7)