TY - JOUR
T1 - Mechanistic studies of nickel(II)-catalyzed direct alcoholysis of 8-aminoquinoline amides
AU - Morimoto, Hiroyuki
AU - Akkad, Walaa
AU - Deguchi, Toru
AU - Ohshima, Takashi
N1 - Funding Information:
This paper is dedicated to Professor Kaoru Fuji on the occasion of his 80th birthday. This work was supported by Grant-in-Aid for Scientific Research on Innovative Areas (JSPS KAKENHI Grant No. JP15H05846 in Middle Molecular Strategy for T.O.) from JSPS, and Basis for Supporting Innovative Drug Discovery and Life Science Research (BINDS) (Grant Number JP18am0101091) from AMED, Uehara Memorial Foundation and Takeda Science Foundation. The computation was carried out using the computer resource offered under the category of General Projects by Research Institute for Information Technology, Kyushu University.
Publisher Copyright:
© 2020 The Japan Institute of Heterocyclic Chemistry.
PY - 2020/1/1
Y1 - 2020/1/1
N2 - This paper describes the mechanistic aspects of nickel(II)-catalyzed direct alcoholysis of 8-aminoquinoline amides. Kinetic experiments suggested that the nickel(II) catalyst existed in an oligomeric form in the resting state, and the 8-aminoquinoline generated after cleavage coordinated to the nickel(II) catalyst to decelerate the reaction. In addition, density functional theory calculations revealed that the reactions proceeded via the intermediate with N,N,O-tridentate coordination of 8-aminoquinoline amides to the nickel(II) metal center, and that the alcoholysis reaction did not involve deprotonation of the N-H bond of 8-aminoquinoline amides, in contrast to the proposed mechanism for C-H bond functionalization reactions of 8-aminoquinoline amides.
AB - This paper describes the mechanistic aspects of nickel(II)-catalyzed direct alcoholysis of 8-aminoquinoline amides. Kinetic experiments suggested that the nickel(II) catalyst existed in an oligomeric form in the resting state, and the 8-aminoquinoline generated after cleavage coordinated to the nickel(II) catalyst to decelerate the reaction. In addition, density functional theory calculations revealed that the reactions proceeded via the intermediate with N,N,O-tridentate coordination of 8-aminoquinoline amides to the nickel(II) metal center, and that the alcoholysis reaction did not involve deprotonation of the N-H bond of 8-aminoquinoline amides, in contrast to the proposed mechanism for C-H bond functionalization reactions of 8-aminoquinoline amides.
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U2 - 10.3987/COM-19-S(F)30
DO - 10.3987/COM-19-S(F)30
M3 - Article
AN - SCOPUS:85078447339
VL - 101
SP - 471
EP - 485
JO - Heterocycles
JF - Heterocycles
SN - 0385-5414
IS - 2
ER -