Issue 10, 2014

A remarkable regiocontrol in the palladium-catalyzed silylstannylation of fluoroalkylated alkynes – highly regio- and stereoselective synthesis of multi-substituted fluorine-containing alkenes

Abstract

On treating fluorine-containing internal alkynes with 1.2 equiv. of (trimethylsilyl)tributyltin in the presence of 2.5 mol% of Pd(PPh3)2Cl2 in THF at the reflux temperature for 6 h, the silylstannylation reaction proceeded smoothly to afford the corresponding silylstannylated adducts in high yields in a highly regio- and cis-selective manner. Switching the palladium catalyst from Pd(PPh3)2Cl2 to Pd(t-BuNC)2Cl2 promoted the formation of silylstannylated adducts with opposite regioselectivity. The thus obtained silylstannylated adducts were subjected to Stille cross-coupling reactions to furnish the corresponding fluoroalkylated vinylsilanes whose C–Si bond was converted to a C–C bond by treating with aldehyde in the presence of TBAF and Zn(OTf)2, the corresponding fluoroalkylated tetra-substituted alkenes being afforded in moderate to good yields with a defined stereochemistry.

Graphical abstract: A remarkable regiocontrol in the palladium-catalyzed silylstannylation of fluoroalkylated alkynes – highly regio- and stereoselective synthesis of multi-substituted fluorine-containing alkenes

Supplementary files

Article information

Article type
Paper
Submitted
19 Sep 2013
Accepted
19 Dec 2013
First published
20 Dec 2013

Org. Biomol. Chem., 2014,12, 1611-1617

A remarkable regiocontrol in the palladium-catalyzed silylstannylation of fluoroalkylated alkynes – highly regio- and stereoselective synthesis of multi-substituted fluorine-containing alkenes

T. Konno, R. Kinugawa, T. Ishihara and S. Yamada, Org. Biomol. Chem., 2014, 12, 1611 DOI: 10.1039/C3OB41903G

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