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Published on: January 30, 2015
Visible-Light-Promoted Trifluoromethylation/Ring-Opening Reaction of Vinylcyclopropanes by an EDA Complex
Yuanyuan Ren1, Ke-Hu Wang1, Bo-Sheng Zhang1
1College of Chemistry and Chemical Engineering, Northwest Normal University, 967 Anning East Road, Lanzhou 730070, P. R. China.
Abstract:
A novel, efficient, and photocatalyst-free method for the 1,5-hydrotrifluoromethylation of vinylcyclopropanes is developed. This transformation is achieved via photoactivation of an electron donor-acceptor (EDA) complex formed between CF3Br and TMEDA. The key selectivity challenge is overcome through a hydrogen atom transfer (HAT) mechanism, which redirects the reaction pathway away from conventional halogen-atom transfer (XAT). This practical, metal-free system exhibits a broad substrate scope and high stereoselectivity. The synthetic utility is further demonstrated through product derivatization, and the proposed mechanism is supported by control experiments and DFT calculations.
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