α-Vinylation of Ester Equivalents via Main Group Catalysis for the Construction of Quaternary Centers

A methodology for the construction of sterically congestedquaternarycenters via the trapping of vinyl carbocations with silyl ketene acetalsis disclosed. This main group-catalyzed & alpha;-vinylation reactionis advantageous as methods to access these congested motifs are limited.Moreover, & beta;,& gamma;-unsaturated carbonyl moieties and tetrasubstitutedalkenes are present in various bioactive natural products and pharmaceuticals,and this catalytic platform offers a means of accessing them usingsimple and inexpensive materials.

Automated summary

This paper presents a methodology for the construction of sterically congested quaternary centers by trapping vinyl carbocations with silyl ketene acetals. This main group-catalyzed α-vinylation reaction is advantageous due to limited methods for accessing these congested motifs. Furthermore, β, γ-unsaturated carbonyl moieties and tetrasubstituted alkenes are commonly found in bioactive natural products and pharmaceuticals, and this catalytic platform provides a simple and cost-effective means of synthesizing them.