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

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 stereoselect...

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Bibliographic Details
Published in:Chemical science (Cambridge) 2019-08, Vol.1 (32), p.7579-7583
Main Authors: Sun, Feng-Na, Yang, Wan-Chun, Chen, Xiao-Bing, Sun, Yu-Li, Cao, Jian, Xu, Zheng, Xu, Li-Wen
Format: Article
Language:English
Subjects:
Activation
Alkynes
Bearing
Bimetals
Chemical industry
Chemical reactions
Copper
Cross coupling
Crystallography
Enantiomers
Fluorine
Ligands
Organic chemistry
Palladium
Stereoselectivity
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Summary: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(sp 2 )-C(sp 3 ) bond cleavage and new C(sp 3 )-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. A highly enantioselective Pd/Cu-catalyzed tandem C-C bond activation/Sonogashira reaction was developed with the aid of new TFSi-Phos, which provided chiral alkynyl indanones in good yields and enantioselectivities.
ISSN:2041-6520
2041-6539
DOI:10.1039/c9sc02431j