Premium
The Mechanism of NO Bond Cleavage in Rhodium‐Catalyzed CH Bond Functionalization of Quinoline N ‐oxides with Alkynes: A Computational Study
Author(s) -
Li Yingzi,
Liu Song,
Qi Zisong,
Qi Xiaotian,
Li Xingwei,
Lan Yu
Publication year - 2015
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201500290
Subject(s) - chemistry , regioselectivity , quinoline , reductive elimination , electrophile , catalysis , bond cleavage , protonation , deprotonation , rhodium , alkyne , oxidative addition , moiety , medicinal chemistry , density functional theory , transition state , leaving group , stereochemistry , computational chemistry , organic chemistry , ion
Metal‐catalyzed CH activation not only offers important strategies to construct new bonds, it also allows the merge of important research areas. When quinoline N‐ oxide is used as an arene source in CH activation studies, the NO bond can act as a directing group as well as an O‐atom donor. The newly reported density functional theory method, M11L, has been used to elucidate the mechanistic details of the coupling between quinoline NO bond and alkynes, which results in CH activation and O‐atom transfer. The computational results indicated that the most favorable pathway involves an electrophilic deprotonation, an insertion of an acetylene group into a RhC bond, a reductive elimination to form an oxazinoquinolinium‐coordinated Rh I intermediate, an oxidative addition to break the NO bond, and a protonation reaction to regenerate the active catalyst. The regioselectivity of the reaction has also been studied by using prop‐1‐yn‐1‐ylbenzene as a model unsymmetrical substrate. Theoretical calculations suggested that 1‐phenyl‐2‐quinolinylpropanone would be the major product because of better conjugation between the phenyl group and enolate moiety in the corresponding transition state of the regioselectivity‐determining step. These calculated data are consistent with the experimental observations.