Acid-Catalyzed Decomposition of O-Silylated α-Diazo-β-hydroxy Esters: Access to Mixed Monosilyl Acetals.

Abstract

Acid-catalyzed decomposition of diazocarbonyl compounds triggers a wide range of transformations leading to synthetically useful building blocks with high diversity. In this field, the chemistry of α-diazo-β-hydroxy ester substrates is largely dominated by migration processes. We describe herein a new approach to original mixed monosilyl acetals from O-protected α-diazo-β-hydroxy-β-aryl esters and alcohols, catalyzed by trimethylsilyl trifluoromethanesulfonate (TMSOTf). The ratio between these original mixed acetals, the symmetric acetals, and the migration products fluctuates depending on the catalyst, the nature of the alcohols, and the substituent on the aromatic ring. Fifty-six examples are reported herein with yields up to 71% and diastereoselectivity up to 6:1. Such mixed monosilyl acetals constitute a synthetic equivalent of α-substituted β-oxoesters with high potential for further transformations.