Azocarboxamide-enabled enantioselective regiodivergent unsymmetrical 1,2-diaminations

Yun-Dong Fu, Han Zhang, Bei-Bei Li, Lihua Huang (), Xiao Xiao, Min-Can Wang, Donghui Wei () and Guang-Jian Mei ()
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Yun-Dong Fu: Zhengzhou University
Han Zhang: Zhengzhou University
Bei-Bei Li: Zhengzhou University
Lihua Huang: Zhengzhou University
Xiao Xiao: Zhejiang University of Technology
Min-Can Wang: Zhengzhou University
Donghui Wei: Zhengzhou University
Guang-Jian Mei: Zhengzhou University

Nature Communications, 2024, vol. 15, issue 1, 1-12

Abstract: Abstract Enantioenriched unsymmetrical vicinal diamines are important basic structural motifs. While catalytic asymmetric intermolecular 1,2-diamination of carbon–carbon double bonds represents the most straightforward approach for preparing enantioenriched vicinal-diamine-containing heterocycles, these reactions are often limited to the installation of undifferentiated amino functionalities through metal catalysis and/or the use of stoichiometric amounts of oxidants. Here, we report organocatalytic enantioselective unsymmetrical 1,2-diaminations based on the rational design of a bifunctional 1,2-diamination reagent, namely, azocarboxamides (ACAs). Under the catalysis of chiral phosphoric acid, unsymmetrical 1,2-diaminations of ACAs with various electron-rich double bonds readily occur in a regiodivergent manner. Indoles prefer dual hydrogen-bonding mode to give dearomative (4 + 2) products, and 3-vinylindoles and azlactones are inclined to undergo unsymmetrical 1,2-diamination via the (3 + 2) process. DFT calculations are performed to reveal the reaction mechanism and the origin of the regio- and enantioselectivity. Guided by computational design, we are able to reverse the regioselectivity of the dearomative unsymmetrical 1,2-diamination of indoles using Lewis acid catalysis.

Date: 2024
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DOI: 10.1038/s41467-024-54598-z

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