Vanadyl species-catalyzed complementary β-oxidative carbonylation of styrene derivatives with aldehydes. Issue 8 (7th January 2015)

• Record Type: Journal Article
• Authors: Yang, Wen-Chieh; Weng, Shiue-Shien; Ramasamy, Anandhan; Rajeshwaren, Gobi; Liao, Yi-Ya; Chen, Chien-Tien
• Is Part Of: Organic & biomolecular chemistry. Volume 13:Issue 8(2015)
• Page Start: 2385
• Page End: 2392
• Publication Date: 2015-01-07
• Subjects: Chemistry, Organic -- Periodicals; Bioorganic chemistry -- Periodicals; Chemistry, Physical organic -- Periodicals; 547
• DOI: 10.1039/c4ob02621g
• Languages: English
• ISSNs: 1477-0520

Abstract

Abstract : By judicious choice of the counter anions in the vanadyl catalysts, we can achieve β-hydroxylated and t -butyl peroxylated carbonylation of styrenes by aromatic 1° and 2° alkyl aldehydes in a complementary manner. Abstract : 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.