Issue 32, 2019

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

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.

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

Supplementary files

Article information

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
Creative Commons BY license

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

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

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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