NiH-Catalyzed Hydroamination/Cyclization Cascade: Rapid Access to Quinolines

Despite the significant success of metal-H-catalyzed hydroamination methodologies, considerable limitations still exist in the selective hydroamination of alkynes, especially for terminal alkynes. Herein, we develop a highly efficient NiH catalytic system that activates readily available alkynes for...

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Bibliographic Details
Published inACS catalysis Vol. 11; no. 13; pp. 7772 - 7779
Main Authors Gao, Yang, Yang, Simin, Huo, Yanping, Chen, Qian, Li, Xianwei, Hu, Xiao-Qiang
Format Journal Article
LanguageEnglish
Published American Chemical Society 02.07.2021
Subjects
anthranils
quinolines
NiH catalysis
alkynes
hydroamination
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Summary:Despite the significant success of metal-H-catalyzed hydroamination methodologies, considerable limitations still exist in the selective hydroamination of alkynes, especially for terminal alkynes. Herein, we develop a highly efficient NiH catalytic system that activates readily available alkynes for a cascade hydroamination/cyclization reaction with anthranils. This mild, operationally simple protocol is amenable to a wide array of alkynes including terminal and internal, aryl and alkyl, electron-deficient and electron-rich ones, delivering structurally diverse quinolines in useful to excellent yields (>80 examples, up to 93% yield). The utility of this procedure is exhibited in the late-stage functionalization of several natural products and in the concise synthesis of an antitumor molecule graveolinine and a triplex DNA intercalator. Preliminary mechanistic experiments suggest an alkenylnickel-mediated alkyne hydroamination and an intramolecular cyclization/aromatization of putative enamine intermediates.
ISSN:2155-5435
2155-5435
DOI:10.1021/acscatal.1c02055