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Transition‐Metal‐Free C(sp 2 )–C(sp 2 ) Cross‐Coupling of Diazo Quinones with Catechol Boronic Esters
Author(s) -
Wu Kai,
Wu LiangLiang,
Zhou CongYing,
Che ChiMing
Publication year - 2020
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.202006542
Subject(s) - diazo , chemistry , catechol , carbene , intramolecular force , density functional theory , coupling reaction , derivatization , medicinal chemistry , combinatorial chemistry , computational chemistry , photochemistry , organic chemistry , high performance liquid chromatography , catalysis
A transition‐metal‐free C(sp 2 )−C(sp 2 ) bond formation reaction by the cross‐coupling of diazo quinones with catechol boronic esters was developed. With this protocol, a variety of biaryls and alkenyl phenols were obtained in good to high yields under mild conditions. The reaction tolerates various functionalities and is applicable to the derivatization of pharmaceuticals and natural products. The synthetic utility of the method was demonstrated by the short synthesis of multi‐substituted triphenylenes and three bioactive natural products, honokiol, moracin M, and stemofuran A. Mechanistic studies and density functional theory (DFT) calculations revealed that the reaction involves attack of the boronic ester by a singlet quinone carbene followed by a 1,2‐rearrangement through a stepwise mechanism.