image: A series of amines, including synthetic challenging primary amines were synthesized with highly tolerance of other reducible functional groups. Mechanistic studies from control experiments and cross-coupling reactions via NMR spectroscopy, operando IR as well as DFT computation reveal a distinct reaction pathway involving aldehyde and amido complex as intermediates. Thus, the current protocol represents a new amide bond activation model that involves C-N bond cleavage-reforming and C-O bond cleavage process. view more
Credit: Chinese Journal of Catalysis
Amines are widely used in pharmaceutical, agrochemical and materials chemistry. Reductive transformation of amides to amines is one of the most promising and straightforward methods for the synthesis of amines, as amides are naturally prevalent or easily accessed via chemical synthesis. However, selective deoxygenative reduction of amides resulting from C–O bond cleavage is challenging. Catalytic hydroboration of C=O bonds has emerged as an efficient methodology to transform carbonyl compounds (ketones, aldehydes, esters, and carbon dioxide) into value-added products (normally O–B compounds without C-O bonds cleavage). However, catalytic deoxygenative hydroboration of carbonyls that resulted from C–O bond cleavage remains limited. Only few catalysts were successfully applied for such transformation. A general catalyst working for primary, secondary, and tertiary amides under mild condition is still limited. In addition, detection and isolation of reaction intermediate and detailed DFT calculations to understand the reaction pathway are lacking in the literature.
Recently, a research team led by Dr. Lipeng Wu from Lanzhou Institute of Chemical Physics (LICP) of the Chinese Academy of Sciences (CAS) and Prof. Haijun Jiao from LIKAT, Rostock, Germany reported an earth-abundant Zr-H catalyst for the effective amine synthesis. Meanwhile, detailed mechanistic studies revealed a distinct reaction pathway of aldehyde and amido complex formation via an unusual C-N bond cleavage-reforming and then C-O bond cleavage process. Extended application to the synthesis of bio- and drug-modified amines is also demonstrated. The results were published in Chinese Journal of Catalysis (DOI: 10.1016/S1872-2067(21)63853-6).
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About the Journal
Chinese Journal of Catalysis is co-sponsored by Dalian Institute of Chemical Physics, Chinese Academy of Sciences and Chinese Chemical Society, and it is currently published by Elsevier group. This monthly journal publishes in English timely contributions of original and rigorously reviewed manuscripts covering all areas of catalysis. The journal publishes Reviews, Accounts, Communications, Articles, Highlights, Perspectives, and Viewpoints of highly scientific values that help understanding and defining of new concepts in both fundamental issues and practical applications of catalysis. Chinese Journal of Catalysis ranks among the top six journals in Applied Chemistry with a current SCI impact factor of 8.271. The Editors-in-Chief are Profs. Can Li and Tao Zhang.
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Chinese Journal of Catalysis