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Ligand‐Assisted Palladium(II)/(IV) Oxidation for sp 3 CH Fluorination
Author(s) -
Sun Huan,
Zhang Yi,
Chen Ping,
Wu YunDong,
Zhang Xinhao,
Huang Yong
Publication year - 2016
Publication title -
advanced synthesis and catalysis
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.541
H-Index - 155
eISSN - 1615-4169
pISSN - 1615-4150
DOI - 10.1002/adsc.201600015
Subject(s) - palladium , chemistry , ligand (biochemistry) , denticity , chelation , surface modification , catalysis , inert , inorganic chemistry , medicinal chemistry , metal , organic chemistry , biochemistry , receptor
The direct functionalization of inert sp 3 CH bonds is limited to a few bond types. Although the activation of sp 3 CH bonds can be accomplished under mild conditions using palladium catalysts, the subsequent functionalization is not trivial due to the high energy required to convert palladium(II) to palladium(IV). We have systematically studied the palladium oxidation using computation‐guided experiments for reactions involving strong chelation control. We find that a mild external ligand could significantly accelerate the oxidation of palladium(II) to palladium(IV) for strong bidentate directing groups. The acceleration is believed to be a result of ligand stabilization of both the palladium(II) and palladium(IV) intermediates.