Issue 4, 2023

Visible-light-induced organocatalytic enantioselective N–H insertion of α-diazoesters enabled by indirect free carbene capture

Abstract

While asymmetric insertion of metal carbenes into H–X (X = C, N, O, etc.) bonds has been well-established, asymmetric control over free carbenes is challenging due to the presence of strong background reactions and lack of any anchor for a catalyst interaction. Here we have achieved the first photo-induced metal-free asymmetric H–X bond insertion of this type. With visible light used as a promoter and a chiral phosphoric acid used as a catalyst, α-diazoesters and aryl amines underwent smooth N–H bond insertion to form enantioenriched α-aminoesters with high efficiency and good enantioselectivity under mild conditions. Key to the success was the use of DMSO as an additive, which served to rapidly capture the highly reactive free carbene intermediate to form a domesticated sulfoxonium ylide.

Graphical abstract: Visible-light-induced organocatalytic enantioselective N–H insertion of α-diazoesters enabled by indirect free carbene capture

Supplementary files

Article information

Article type
Edge Article
Submitted
15 sep 2022
Accepted
28 nov 2022
First published
29 nov 2022
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2023,14, 843-848

Visible-light-induced organocatalytic enantioselective N–H insertion of α-diazoesters enabled by indirect free carbene capture

W. Guo, Y. Zhou, H. Xie, X. Yue, F. Jiang, H. Huang, Z. Han and J. Sun, Chem. Sci., 2023, 14, 843 DOI: 10.1039/D2SC05149D

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