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Published on: November 30, 2022
Synthesis of constrained bicycloalkanes through bibase-promoted brook rearrangement/radical-polar crossover
Xinke Ouyang1, Bingyao Shi1, Yuanyuan Zhao1
1State Key Laboratory of Green Pesticide, Engineering Research Center of Photoenergy Utilization for Pollution Control and Carbon Reduction, CCNU-uOttawa Joint Research Centre, College of Chemistry, Central China Normal University (CCNU) 152 Luoyu Road Wuhan Hubei 430079 China chaoshu@ccnu.edu.cn.
Abstract:
Highly constrained bicyclic scaffolds are ubiquitous and attracting increasing interest in pharmaceutical and biotechnology discoveries owing to the enhanced activities. Herein, we report a protocol to access highly substituted constrained bicycloalkanes from readily accessible α-silyl alcohols and olefins through a bibase-promoted Brook rearrangement/radical-polar crossover cyclization (RPCC) process. Of note, the practical procedure features broad substrate scope and good group tolerance under mild and operationally simple conditions, using an inexpensive organic photocatalyst. Gram-scale preparation and diverse synthetic transformations demonstrate opportunities to rapidly construct molecular complexity. Mechanistic studies have indicated that the transformation involves a bibase-promoted radical transfer rearrangement addition/radical-polar crossover cyclization relay sequence, which differs from traditional solitary RPCC reactions.
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