α-silyloxyaldehydes are common chiral building blocks in natural product synthesis, yet their preparations are often limited to structures that are available by modification of naturally occurring α-hydroxy or α-amino acids.<br/>More general preparations are available, but may suffer from troublesome reductions of corresponding cyanohydrins or undesirable step economies. We previously introduced a silyl cation-induced ring-opening of racemic enol ester epoxides that addressed the step economy, accessing α-silyloxyaldehydes in three steps from alkynes. Here we describe an enantioselective variant of this sequence employing catalytic asymmetric epoxidation of enol esters. Microwave-enhanced silyl cation-induced ring opening of the enantioenriched enol ester epoxides proceeds with retention of configuration, furnishing α-siloxyaldehydes with different silyl protecting groups.

Asymmetric Catalysis in a three-step Synthesis of α-silyloxyaldehydes from Hydrocarbons

ACS Spring Meeting 2021

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