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 Sept. 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

This article is licensed under a Creative Commons Attribution-NonCommercial 3.0 Unported Licence. You can use material from this article in other publications, without requesting further permission from the RSC, provided that the correct acknowledgement is given and it is not used for commercial purposes.

To request permission to reproduce material from this article in a commercial publication, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party commercial publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements