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Intramolecular C(sp 3 )–H Bond Oxygenation by Transition‐Metal Acylnitrenoids
Author(s) -
Tan Yuqi,
Chen Shuming,
Zhou Zijun,
Hong Yubiao,
Ivlev Sergei,
Houk K. N.,
Meggers Eric
Publication year - 2020
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.202009335
Subject(s) - intramolecular force , amination , regioselectivity , chemistry , nitrene , ruthenium , enantioselective synthesis , catalysis , allylic rearrangement , stereochemistry , transition metal , medicinal chemistry , organic chemistry
This study demonstrates for the first time that easily accessible transition‐metal acylnitrenoids can be used for controlled direct C(sp 3 )‐H oxygenations. Specifically, a ruthenium catalyst activates N‐benzoyloxycarbamates as nitrene precursors towards regioselective intramolecular C−H oxygenations to provide cyclic carbonates, hydroxylated carbamates, or 1,2‐diols. The method can be applied to the chemoselective C−H oxygenation of benzylic, allylic, and propargylic C(sp 3 )−H bonds. The reaction can be performed in an enantioselective fashion and switched in a catalyst‐controlled fashion between C−H oxygenation and C−H amination. This work provides a new reaction mode for the regiocontrolled and stereocontrolled conversion of C(sp 3 )‐H into C(sp 3 )−O bonds.