Publication
Bicyclo[1.1.1]pentanes (BCPs) are well‐studied bioisosteres for para‐substituted benzene rings and numerous methods for synthesizing 1,3‐difunctionalized BCPs have been developed. However, synthetic approaches to access vinyl BCP motifs remain limited, with only few reports on the synthesis of BCP‐olefins bearing heteroatom substituents. Herein, we present the synthesis of BCP‐substituted enamides, enol ethers, and vinyl sulfides through the sequential functionalization of ethynylbenziodoxolone (EBX) reagents containing a BCP scaffold. Stereoselective addition of a nucleophile generates heteroatomic Z‐vinylbenziodoxolone (VBX) reagents. The hypervalent iodine substituent of the VBX reagents serves then as a versatile platform for further arylation, vinylation, and trifluoromethylation. This method provides a modular synthesis of previously inaccessible heteroatom‐substituted vinyl BCPs.