Radical Functionalization of 1,6‐Diene via Transannular Cyano Migration: Synthesis of Polysubstituted Cyclopentanes^†

2024/11/21 by Ziqiang Wang, Yasu Chen, Chen Zhu
Chemistry · Pharmacology, Toxicology and Pharmaceutics · #Asymmetric Synthesis and Catalysis #Fluorine in Organic Chemistry #Radical Photochemical Reactions

paper · pdf · doi:10.1002/cjoc.202401072

openalex publication_date 2024/11/21 · openalex created_date 2025/10/10 · openalex updated_date 2026/07/30

Abstract

Comprehensive Summary An efficient transannular cyano migration is reported for gem ‐dicyano‐1,6‐diene, which is triggered by the addition of external arylsulfonyl radicals. The overall transformation proceeds through a sequence of intramolecular 5‐exo‐trig cyclization, suprafacial 1,4‐cyano migration, and the capture by H or D atom, leading to the production of valuable polysubstituted cyclopentanes under mild photoredox catalytic conditions. The reaction is adapted to a wide range of sodium (hetero)arylsulfinates, demonstrating good functional group compatibility. This method provides a new protocol for radical‐mediated functional group migration.

Citations

• Radical-mediated difunctionalization of unactivated alkenes through distal migration of functional groups
• Radical-Mediated Remote Functional Group Migration
• Radical Heteroarylation of Alkenes and Alkanes via Heteroaryl Migration

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