Cocatalyst-Dependent Divergent Amination of Alkylgold Intermediates with Azodicarboxylates

IF 11.3 1区化学 Q1 CHEMISTRY, PHYSICAL

ACS Catalysis Pub Date : 2025-03-12 DOI:10.1021/acscatal.5c00495

Yuan Haoxuan, Ming Bao, Kewei Chen, Jingjing Huang, Yue Pan, Dorota Gryko, Xinfang Xu

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Abstract

The asymmetric electrophilic amination using azodicarboxylates as the N-source for the construction of the C–N bond has attracted much attention over the past decades. However, the use of in situ formed nucleophilic intermediates, rather than bench-stable reagents, for the asymmetric amination remains elusive and challenging. Herein, we disclose an enantioselective electrophilic amination reaction of in situ generated alkylgold species with azodicarboxylates under a gold complex and chiral quinine-derived squaramide (QN-SQA) synergetic catalysis, leading to chiral alkylideneoxazolines with a nitrogen-containing tertiary carbon stereocenter in good to high yields and enantioselectivities. Moreover, starting from the same reagents, the oxazoles incorporating an aminomethyl group on the 5-position could be obtained by gold and Brønsted acid relay catalysis via alkylideneoxazoline species. This method offers a complementary approach for the electrophilic amination through interception of in situ formed alkylgold species. With this strategic protocol, further synthetic applications can be envisioned for the catalytic construction of C–C and C–X bonds.

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来源期刊

ACS Catalysis CHEMISTRY, PHYSICAL-

CiteScore

20.80

自引率

6.20%

发文量

1253

审稿时长

1.5 months

期刊介绍： ACS Catalysis is an esteemed journal that publishes original research in the fields of heterogeneous catalysis, molecular catalysis, and biocatalysis. It offers broad coverage across diverse areas such as life sciences, organometallics and synthesis, photochemistry and electrochemistry, drug discovery and synthesis, materials science, environmental protection, polymer discovery and synthesis, and energy and fuels. The scope of the journal is to showcase innovative work in various aspects of catalysis. This includes new reactions and novel synthetic approaches utilizing known catalysts, the discovery or modification of new catalysts, elucidation of catalytic mechanisms through cutting-edge investigations, practical enhancements of existing processes, as well as conceptual advances in the field. Contributions to ACS Catalysis can encompass both experimental and theoretical research focused on catalytic molecules, macromolecules, and materials that exhibit catalytic turnover.