Iron‐Catalyzed Alkenylzincation of Internal Alkynes†

Comprehensive Summary The alkenylzincation of internal alkynes is an effective method for the synthesis of multi‐substituted conjugated dienes; however, the current catalytic systems for this reaction are limited in terms of substrate scope and selectivity control, which restricts its practical applications. Herein, we report the first iron‐catalyzed alkenylzincation of internal alkynes, which features mild conditions, simple operation, broad substrate scope (including aryl/alkyl, diaryl, and dialkyl acetylenes), excellent functional group tolerance (tolerating highly active functional groups such as ester, methylthio, amide, sulfonyl, cyano, etc .), and high activity (with a turnover number of up to 11500, the highest record for carbometallation reactions). Notably, the catalytic system described in this article also realized the highly selective vinylzincation of unfunctionalized internal alkynes as well as the alkenylzincation of unsymmetrical diarylacetylenes and dialkyl acetylenes, which have not been achieved with other catalytic systems reported in the literatures. The current study provides a highly selective access to synthetically important multi‐substituted conjugated dienes.