Chiral Bifunctional Phosphine Ligand Enabling Gold-Catalyzed Asymmetric Isomerization of Alkyne to Allene and Asymmetric Synthesis of 2,5-Dihydrofuran

Journal of the American Chemical Society
Xinpeng ChengLiming Zhang

Abstract

The asymmetric isomerization of alkyne to allene is the most efficient and the completely atom-economic approach to this class of versatile axial chiral structure. However, the state-of-the-art is limited to tert-butyl alk-3-ynoate substrates that possess requisite acidic propargylic C-H bonds. Reported here is a strategy based on gold catalysis that is enabled by a designed chiral bifunctional biphenyl-2-ylphosphine ligand. It permits isomerization of alkynes with nonacidic α-C-H bonds and hence offers a much-needed general solution. With chiral propargylic alcohols as substrates, 2,5-disubstituted 2,5-dihydrofurans are formed in one step in typically good yields and with good to excellent diastereoselectivities. With achiral substrates, 2,5-dihydrofurans are formed with good to excellent enantiomeric excesses. A novel center-chirality approach is developed to achieve a stereocontrol effect similar to an axial chirality in the designed chiral ligand. The mechanistic studies established that the precatalyst axial epimers are all converted into the catalytically active cationic gold catalyst owing to the fluxional axis of the latter.

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Citations

Jul 11, 2019·Organic & Biomolecular Chemistry·Wen-Bo Shen, Xiang-Ting Tang
Sep 26, 2019·Organic & Biomolecular Chemistry·Taoda ShiWenhao Hu
Jan 3, 2021·Chemistry, an Asian Journal·Jia-Jun Jiang, Man-Kin Wong
Feb 9, 2021·Chemical Reviews·Chetan C ChintawarNitin T Patil
Feb 10, 2021·Chemical Reviews·Raquel P Herrera, M Concepción Gimeno
Feb 13, 2021·Angewandte Chemie·Inmaculada Martín-TorresAntonio M Echavarren
May 6, 2021·Chemistry : a European Journal·Robert J HarrisRoss A Widenhoefer
Apr 4, 2020·Organic Letters·Qinxuan Wang, Jeremy A May
Jul 24, 2020·The Journal of Organic Chemistry·Moustapha FortunatoFlorian Jaroschik
Nov 19, 2020·Journal of the American Chemical Society·Hanbyul KimSeunghoon Shin
Aug 1, 2019·The Journal of Organic Chemistry·Xinpeng ChengLiming Zhang
Jul 11, 2019·Journal of the American Chemical Society·Giuseppe ZuccarelloAntonio M Echavarren
Sep 3, 2021·ChemPlusChem·Giuseppe ZuccarelloAntonio M Echavarren
Dec 4, 2021·Chemical Reviews·Jennifer L KennemurBenjamin List

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