期刊
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
卷 140, 期 23, 页码 7292-7300出版社
AMER CHEMICAL SOC
DOI: 10.1021/jacs.8b03626
关键词
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资金
- JSPS KAKENHI [16KT0057, 17H03057, JP15H00943, JP15H05803]
- Frontier Research Base for Global Young Researchers, Osaka University on the program of MEXT
Given the growing demand for green and sustainable chemical processes, the catalytic reductive alkylation of amines with main-group catalysts of low toxicity and molecular hydrogen as the reductant would be an ideal method to functionalize amines. However, such a process remains challenging. Herein, a novel reductive alkylation system using H-2 is presented, which proceeds via a tandem reaction that involves the B(2,6-Cl2C6H3)(p-HC6F4)(2)-catalyzed formation of an imine and the subsequent hydrogenation of this imine catalyzed by a frustrated Lewis pair (FLP). This reductive alkylation reaction generates H2O as the sole byproduct and directly functionalizes amines that bear a remarkably wide range of substituents including carboxyl, hydroxyl, additional amino, primary amide, and primary sulfonamide groups. The synthesis of isoindolinones and aminophthalic anhydrides has also been achieved by a one-pot process that consists of a combination of the present reductive alkylation with an intramolecular amidation and intramolecular dehydration reactions, respectively. The reaction showed a zeroth-order and a first-order dependence on the concentration of an imine intermediate and B(2,6-Cl2C6H3)(p-HC6F4)(2) respectively. In addition, the reaction progress was significantly affected by the concentration of H-2. These results suggest a possible mechanism in which the heterolysis of H-2 is facilitated by the FLP comprising THF and B(2,6-Cl2C6H3)(p-HC6F4)(2).
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