Photocatalyzed Diastereoselective Isomerization of Cinnamyl Chlorides to Cyclopropanes.

Journal of the American Chemical Society
Bin XuUttam K Tambar

Abstract

Endergonic isomerizations are thermodynamically unfavored processes that are difficult to realize under thermal conditions. We report a photocatalytic and diastereoselective isomerization of acyclic cinnamyl chlorides to strained cyclopropanes. Quantum mechanical calculations (uM06-2X and DLPNO), including TD-DFT calculations, and experimental studies provide evidence for the energy transfer from an iridium photocatalyst to the allylic chloride substrate followed by C-Cl homolytic cleavage. Subsequent Cl• radical migration forms a localized triplet 1,3-diradical intermediate that, after intersystem crossing, undergoes ring-closing to form the desired product. The mild reaction conditions are compatible with a broad range of functional groups to generate chlorocyclopropanes in high yields and diastereoselectivities. A more efficient process is developed by addition of a catalytic amount of a nickel complex, and we propose a novel role for this cocatalyst to recycle an allyl chloride byproduct generated in the course of the reaction. The reaction is also shown to be stereoconvergent, as an E/Z mixture of cinnamyl chlorides furnish the anti-chlorocyclopropane product in high diastereoselectivity. We anticipate that the use of a vi...Continue Reading

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Citations

Aug 11, 2020·The Journal of Chemical Physics·Sara A M WehlinGerald J Meyer
Oct 7, 2020·Chemical Communications : Chem Comm·Ryo ShintaniKentaro Shirota
Aug 28, 2021·Chemical Reviews·Tomáš NeveselýRyan Gilmour
Jan 13, 2021·Journal of the American Chemical Society·Jakob B BilgerOliver S Wenger
Oct 15, 2021·The Journal of Organic Chemistry·Yan ZhangYijian Rao

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