Enantioselective palladium/copper-catalyzed C–C σ-bond activation synergized with Sonogashira-type C(sp3)–C(sp) cross-coupling alkynylation

Enantioselective palladium/copper-catalyzed C–C σ-bond activation synergized with Sonogashira-type C(sp³)–C(sp) cross-coupling alkynylation†

Feng-Na Sun,^a Wan-Chun Yang,^a Xiao-Bing Chen,^a Yu-Li Sun,^a Jian Cao,*^a Zheng Xu^a and Li-Wen Xu

*^ab

* Corresponding authors

^a Key Laboratory of Organosilicon Chemistry and Material Technology of Ministry of Education, Key Laboratory of Organosilicon Material Technology of Zhejiang Province, Hangzhou Normal University, P. R. China
E-mail: caojian@hznu.edu.cn, liwenxu@hznu.edu.cn

^b State Key Laboratory for Oxo Synthesis and Selective Oxidation, Suzhou Research Institute, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, P. R. China

Abstract

The Sonogashira-type cross-coupling reaction is one of the most significant alkynylation transformations in organic chemistry. However, highly enantioselective alkynylation via the Sonogashira-type cross-coupling reaction is rather limited, mainly due to the difficulties in matching the stereoselective induction of chiral ligands with the combinational behavior of Pd/Cu-based bimetallic catalysts. We herein report novel enantioselective palladium/copper-catalyzed alkyl alkynylation of cyclobutanones with terminal alkynes via tandem C–C bond activation/Sonogashira-type cross coupling reaction, in which a novel chiral TADDOL-derived phosphoramidite ligand bearing fluorine and silicon-based bulky groups simplified as TFSi-Phos is found to be an efficient ligand for both C(sp²)–C(sp³) bond cleavage and new C(sp³)–C(sp) bond formation. A wide range of chiral alkynylated indanones bearing an all-carbon quaternary stereocenter are obtained efficiently with up to 97.5 : 2.5 er.

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Article information

DOI: https://doi.org/10.1039/C9SC02431J
Article type: Edge Article
Submitted: 19 May 2019
Accepted: 20 Jun 2019
First published: 21 Jun 2019
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry

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Chem. Sci., 2019,10, 7579-7583

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Enantioselective palladium/copper-catalyzed C–C σ-bond activation synergized with Sonogashira-type C(sp³)–C(sp) cross-coupling alkynylation

F. Sun, W. Yang, X. Chen, Y. Sun, J. Cao, Z. Xu and L. Xu, Chem. Sci., 2019, 10, 7579 DOI: 10.1039/C9SC02431J

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