Synthesis of Bicyclo[1.1.1]Pentane Z‐Substituted Enamides, Enol Ethers, and Vinyl Sulfides Using Iodine (III) Reagents

N Najung Lee (Laboratory of Catalysis and Organic Synthesis Institute of Chemical Sciences and Engineering, École Polytechnique Fédérale de Lausanne Lausanne CH‐1015 Switzerland) J Jonas Dechent (Laboratory of Catalysis and Organic Synthesis Institute of Chemical Sciences and Engineering, École Polytechnique Fédérale de Lausanne Lausanne CH‐1015 Switzerland) E Elija Grinhagena (Laboratory of Catalysis and Organic Synthesis Institute of Chemical Sciences and Engineering, École Polytechnique Fédérale de Lausanne Lausanne CH‐1015 Switzerland) J Jerome Waser (Laboratory of Catalysis and Organic Synthesis)

Abstract

Abstract 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.

Article Details

Volume / Issue Vol. 64, Issue 32
Published August 04, 2025
ISSN 1433-7851
Publisher Wiley

Journal Info

Angewandte Chemie International Edition

Wiley

ISSN: 1433-7851 Physical Sciences

Authors (4)

N

Najung Lee

Laboratory of Catalysis and Organic Synthesis Institute of Chemical Sciences and Engineering, École Polytechnique Fédérale de Lausanne Lausanne CH‐1015 Switzerland

J

Jonas Dechent

Laboratory of Catalysis and Organic Synthesis Institute of Chemical Sciences and Engineering, École Polytechnique Fédérale de Lausanne Lausanne CH‐1015 Switzerland

E

Elija Grinhagena

Laboratory of Catalysis and Organic Synthesis Institute of Chemical Sciences and Engineering, École Polytechnique Fédérale de Lausanne Lausanne CH‐1015 Switzerland

J

Jerome Waser

Laboratory of Catalysis and Organic Synthesis