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Decarboxylative Redox Bicyclo[1.1.1]pentylation: Benchmarking the Influence of Backbone Substituents on C-C

Stacie K Nelson¹, Austin Pounder¹, Alexandra E Thwaites¹

¹Canadian Centre for Research in Advanced Fluorine Technologies and Department of Chemistry and Biochemistry, University of Lethbridge, 4401 University Drive West, Lethbridge, AB T1K 3M4, Canada.

Organic Letters

|December 4, 2025

Abstract:

The allylic substitution of α-(trifluoromethyl)styrenes was used to assess the feasibility of C-C bond formation to the bridgehead of bicyclo[1.1.1]pentanes via redox-active esters that fragment upon single-electron reduction. We observed that a 3-fluoro substituent on the backbone of the bicyclo[1.1.1]pentane induces behavior distinct from that with other electron-withdrawing groups as seen through diminished yields. The experimental results were supplemented with complementary computational studies to gain insights into the phenomena causing this dichotomy.

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