Boron-enabled geometric isomerization of alkenes via selective energy-transfer catalysis

Science
John J MolloyRyan Gilmour

Abstract

Isomerization-based strategies to enable the stereodivergent construction of complex polyenes from geometrically defined alkene linchpins remain conspicuously underdeveloped. Mitigating the thermodynamic constraints inherent to isomerization is further frustrated by the considerations of atom efficiency in idealized low-molecular weight precursors. In this work, we report a general ambiphilic C3 scaffold that can be isomerized and bidirectionally extended. Predicated on highly efficient triplet energy transfer, the selective isomerization of β-borylacrylates is contingent on the participation of the boron p orbital in the substrate chromophore. Rotation of the C(sp2)-B bond by 90° in the product renders re-excitation inefficient and endows directionality. This subtle stereoelectronic gating mechanism enables the stereocontrolled syntheses of well-defined retinoic acid derivatives.

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Citations

Sep 26, 2020·Angewandte Chemie·Max WienholdRyan Gilmour
Nov 6, 2020·Organic & Biomolecular Chemistry·Bing-Xue ShenQing-An Chen
Mar 7, 2021·Nature Communications·Eiji KudoTetsuro Murahashi
Sep 19, 2020·Organic Letters·Thibaud BrégentThomas Poisson
Aug 20, 2021·Chemistry : a European Journal·Thibaud BrégentThomas Poisson
Aug 28, 2021·Chemical Reviews·Tomáš NeveselýRyan Gilmour
Jan 13, 2021·Journal of the American Chemical Society·Jakob B BilgerOliver S Wenger
Jul 11, 2021·Angewandte Chemie·Ziyong WangShih-Yuan Liu
Aug 11, 2021·Chemistry : a European Journal·Pan-Pan GaoJia-Rong Chen
Oct 1, 2021·Journal of the American Chemical Society·Min-Jie ZhouZheng Huang
Nov 6, 2021·Nature Chemistry·Dario Filippini, Mattia Silvi

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