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Palladium‐Catalyzed Picolinamide‐Directed Acetoxylation of Unactivated γ‐C( sp 3 )H Bonds of Alkylamines
Author(s) -
Li Qiong,
Zhang ShuYu,
He Gang,
Nack William A.,
Chen Gong
Publication year - 2014
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.201400121
Subject(s) - chemistry , palladium , amination , intramolecular force , catalysis , yield (engineering) , amine gas treating , medicinal chemistry , surface modification , combinatorial chemistry , organic chemistry , stereochemistry , materials science , metallurgy
We report a new protocol for palladium‐catalyzed acetoxylation of the γ‐C( sp 3 )H bonds of N ‐alkylpicolinamide substrates using PhI(OAc) 2 oxidant. These reactions involve the use of substoichiometric amounts of Li 2 CO 3 additive, which effectively suppresses the competing intramolecular CH amination process. Under these conditions, N ‐propylpicolinamides bearing α substituents can be cleanly converted to γ‐acetoxylated amine products in excellent yield. This CH acetoxylation can also be used in concert with other Pd‐catalyzed picolinamide‐directed CH functionalization reactions for rapid scaffold diversification.