SYNTHESIS OF ALLENES BY 1,6-ADDITION OF ORGANOCUPRATES TO POLARIZED ENYNES

Ten β‐allenic esters, ketones, and thioesters 15 bearing alkyl, alkenyl, aryl, and trimethylsilyl groups are synthesized in 57‐ 85% yield by 1,6‐addition of organocuprates to polarized enynes 10. The dependence of the regioselectivity of the protonation of the allenyl enolate intermediate 7 on the protonating agent is studied: pure allenes are obtained by quenching the intermediate with pivalic acid at −80°C. The method is applied in a short synthesis of pseudoionone (18). Copyright © 1990 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim