Palladium‐Catalyzed Direct Acylation of Ketoximes and Aldoximes from the Alcohol Oxidation Level through C–H Bond Activation

Abstract

A highly efficient palladium‐catalyzed oxidative ortho‐acylation of O‐methyl ketoximes and O‐methyl aldoximes with benzylic and aliphatic alcohols from the alcohol oxidation level is described. This protocol potentially provides new opportunities to use readily available alcohols as starting materials for catalytic reactions, and represents a catalytic alternative to transcend the barriers imposed by classical Friedel–Crafts acylation.

Redox-Induced Aromatic C–H Bond Functionalization in Metal Complex Catalysis from the Electrochemical Point of View

“…Thus, it is obvious that such weak oxidants as oxygen (−0.78 to −1.26 V), 1,4-benzoquinone (0.16 to −0.875V) are not able to oxidize many palladacycles even up to Pd(III) (~0.25 to 1.4 V) complexes, the more so to Pd(IV) (~1.0 to 1.6V) [25]. This explains the numerous failed attempts to use them in such Pd-catalysed C-H functionalizations, such as 1,4-benzoquinone [27][28][29]75,[82][83][84][85], and O 2 [77,82,[86][87][88] for example.…”

Transition Metal‐Catalyzed Reactions Involving Oximes

“…In 2013, Kim et al. described a palladium‐catalyzed oxidative ortho ‐acylation of oxime ethers with alcohols (Scheme ) . A series of substituted O ‐methyl ketoximes and aldoximes was applied to couple with various benzylic and aliphatic alcohols, giving the products in moderate to good yields (Scheme ).…”

Palladium-Catalyzed Decarboxylative Ortho-Ethoxycarbonylation of O-Methyl Ketoximes and 2-Arylpyridines with Potassium Oxalate Monoester

“…Then the Che group described the ortho -amidation of O -methyl ketoximes . Many other functionalizations of O -methyl ketoximes including arylation, , ethoxycarbonylation, acylation, nitration, , cyanation, and other transformations were also demonstrated.…”