The Synthesis of β,γ‐ and α,β‐Unsaturated Aldehydes via Polyene Epoxides

Abstract
A substitute for the Darzens glycidic ester synthesis for converting unsaturated ketones or aldehydes into the homologated β,γ‐ or α,β‐unsaturated aldehydes employing sulfur ylides is described. The carbonyl group is converted into the unsaturated oxirane which is then rearranged to the new aldehyde. High yields of isomerically pure aldehydes are available by this method and the process is of practical importance in the conversion of β‐ionone into the β‐C14‐aldehyde, a key intermediate in the Isler synthesis of vitamin A. The efficient preparation of α‐ and β‐cyclocitral by the novel process is also described.

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