199434-50-9Relevant articles and documents
Methyl ketone oxime esters as nucleophilic coupling partners in Pd-catalyzed C-H alkylation and application in the synthesis of isoquinolines
Zhang, Zhi-Wei,Lin, Aijun,Yang, Jiong
, p. 7041 - 7050 (2014/08/18)
Methyl ketone oxime esters have been found to be excellent coupling partners for C(sp2)-C(sp3) bond formation via Pd-catalyzed aromatic C-H activation. This transformation forms the basis of an approach to regioselectively synthesize substituted isoquinolines via coupling with aryloxime esters. Our mechanistic studies suggested that the reaction proceeded through Pd(II)-catalyzed aromatic C-H activation, tautomerization, and a 1,3-shift of the palladacycle-ligated methyl ketone oxime ester to enable the C-C bond formation by reductive elimination, and intramolecular condensation of an imido-Pd(II) intermediate to form the heterocycle. The aryloxime group not only was used as a directing group for Pd-catalyzed aromatic C-H activation but also functioned as an internal oxidant to allow the reaction to be redox-neutral. Our study illuminated the scope and limitations of this C-H alkylation process, which may serve as the point of departure for developing other C-H functionalization reactions using oxime esters and potentially other carbonyl derivatives as the nucleophilic coupling partners.
Double nucleophilic N-alkylation of α-oxime-esters with Grignard reagents
Mizutani, Yusuke,Tanimoto, Hiroki,Morimoto, Tsumoru,Nishiyama, Yasuhiro,Kakiuchi, Kiyomi
supporting information, p. 5903 - 5906,4 (2020/08/20)
Double nucleophilic N-alkylation of α-oxime-esters, affording N,N-dialkyl-α-amino acids is herein described. Grignard reagents accomplished double N-alkylations via umpolung and various N,N-dialkylated α-amino acids were successfully synthesized in 15 min. Both electron-withdrawing sulfonyl groups and electron-donating silyl and methyl groups on oximes were available. Alkylmagnesium species and (E)-configuration of α-oxime-ester were essential to this cascade reaction.
