Issue 40, 2019

Tertiary amine-directed and involved carbonylative cyclizations through Pd/Cu-cocatalyzed multiple C–X (X = H or N) bond cleavage

Abstract

A novel Pd/Cu-cocatalyzed carbonylative cyclization by C–H activation and N-dealkylative C–N bond activation has been developed for the chemoselective construction of synthetically useful heterocycles. The N,N-dimethylamine group on o-indolyl-N,N-dimethylarylamines was found to act as both the directing group and reactive component in this C–H carbonylative cyclization reaction. Furthermore, a unique C–H oxidation/carbonylative lactonization of diarylmethylamines is firstly demonstrated under modified reaction conditions, which could be easily applicable to the one-step synthesis of multi-substituted phthalides bearing an N,O-ketal skeleton that is difficult to access by previously reported methods. Mechanistic studies implicate that Pd/Cu-cocatalyzed C–H oxidation/carbonylative lactonization is a sequential reaction system via Cu-catalyzed C(sp3)–H oxidation and Pd-catalyzed oxidative carbonylation of the C(sp2)–H bond. It was found that trace amounts of water are essential to promote the Cu-catalyzed C(sp3)–H oxidation of diarylmethylamine for the formation of the hydroxyl group, which could act as an in situ-formed directing group in the intramolecular carbonylative lactonization step.

Graphical abstract: Tertiary amine-directed and involved carbonylative cyclizations through Pd/Cu-cocatalyzed multiple C–X (X = H or N) bond cleavage

Supplementary files

Article information

Article type
Edge Article
Submitted
22 Jun 2019
Accepted
17 Aug 2019
First published
19 Aug 2019
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., 2019,10, 9292-9301

Tertiary amine-directed and involved carbonylative cyclizations through Pd/Cu-cocatalyzed multiple C–X (X = H or N) bond cleavage

Q. Mu, Y. Nie, X. Bai, J. Chen, L. Yang, Z. Xu, L. Li, C. Xia and L. Xu, Chem. Sci., 2019, 10, 9292 DOI: 10.1039/C9SC03081F

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