Vanadyl species-catalyzed complementary β-oxidative carbonylation of styrene derivatives with aldehydes

A series of oxometallic species and metal acetylacetonates (acac) was examined as catalysts for oxidative carbonylation of styrene with benzaldehyde using t-butylhydroperoxide as the co-oxidant in warm acetonitrile. Among them, VO((acac)2 and vanadyl(IV) chloride were found to be the only catalyst c...

Full description

Saved in:
Bibliographic Details
Published in:Organic & biomolecular chemistry 2015-01, Vol.13 (8), p.2385-2392
Main Authors: Yang, Wen-Chieh, Weng, Shiue-Shien, Ramasamy, Anandhan, Rajeshwaren, Gobi, Liao, Yi-Ya, Chen, Chien-Tien
Format: Article
Language:English
Citations: Items that this one cites
Items that cite this one
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
Summary:A series of oxometallic species and metal acetylacetonates (acac) was examined as catalysts for oxidative carbonylation of styrene with benzaldehyde using t-butylhydroperoxide as the co-oxidant in warm acetonitrile. Among them, VO((acac)2 and vanadyl(IV) chloride were found to be the only catalyst class to achieve cross-coupling processes by judiciously tuning the ligand electronic attributes, leading to β-hydroxylation- and β-peroxidation-carbonylation of styrene, respectively, in a complementary manner. Mechanistic studies indicated that vanadyl-associated acyl radicals generated by t-butoxy radical-assisted, homolytic cleavage of the aldehyde C-H bond were involved in tandem processes with an exclusive syn diastereoselectivity in the case of β-methylstyrene.
ISSN:1477-0520
1477-0539
DOI:10.1039/c4ob02621g