Three Component syn‐1,2‐Arylmethylation of Internal Alkynes**

Abstract

AbstractA Pd‐catalyzed three‐component syn‐1,2‐arylmethylation of internal alkynes (ynamides/yne‐acetates/alkynes) is described. The readily available and bench stable coupling partners iodo‐arenes, and methyl boronic acid are successfully used in this coupling strategy to access the methyl‐containing tetra‐substituted olefins; the scope is broad showing excellent functional‐group tolerance. Notably, the transformation is regio‐ as well as stereoselective. The biologically relevant motifs (BRM) bearing iodo‐arenes and ynamides are also used for the late‐stage syn‐1,2‐arylmethylation of alkynes. Aryl‐alkylation, aryl‐trideuteriomethylation, alkynyl‐methylation, and alkenyl‐methylation of ynamides are also presented. The Me‐substituted alkenes are further transformed into synthetically important β‐amino‐indenones and α‐fluoro‐α′‐methyl ketones.