title: Synthesis of enyne and aryl vinyl sulfoxides: functionalization via Pummerer rearrangement.
abstract: An efficient methodology for the synthesis of aryl-substituted vinyl sulfoxides through direct substitution of aryl-substituted alkynyl grignard reagents on menthyl-p-toluenesulfinate followed by Suzuki-Miyaura cross-coupling reaction has been developed. It has also been described that the reaction of alkyl-substituted and cycloalkyl-substituted alkynyl grignard reagents with menthyl-p-toluenesulfinate led to two products, i.e., alkynyl sulfoxide derivatives, as a result of substitution, and enyne sulfoxide derivatives, which resulted from substitution followed by Michael type addition. It was possible to selectively synthesize the enyne sulfoxide derivatives by changing the concentration of the grignard reagent. These alkenyl sulfoxides were transformed into the corresponding [Formula: see text]-thio aldehydes in high yields via additive Pummerer rearrangement.
authors.affiliation: Departamento de Farmácia, Faculdade de Ciências Farmacêuticas, Universidade de São Paulo, São Paulo, SP, Brazil.
authors.forename: Frederico B
authors.initials: FB
authors.lastname: Souza
authors.affiliation: Instituto de Química, Universidade de São Paulo, São Paulo, SP, Brazil.
authors.forename: Anwar
authors.initials: A
authors.lastname: Shamim
authors.affiliation: Departamento de Farmácia, Faculdade de Ciências Farmacêuticas, Universidade de São Paulo, São Paulo, SP, Brazil.
authors.forename: Luiz M Z
authors.initials: LM
authors.lastname: Argomedo
authors.affiliation: Instituto Butantã, São Paulo, SP, Brazil.
authors.forename: Daniel C
authors.initials: DC
authors.lastname: Pimenta
authors.affiliation: Departamento de Farmácia, Faculdade de Ciências Farmacêuticas, Universidade de São Paulo, São Paulo, SP, Brazil. hstefani@usp.br.
authors.forename: Hélio A
authors.initials: HA
authors.lastname: Stefani
mesh_terms: D000447:Aldehydes / Q000737:chemistry; D015394:Molecular Structure; D013237:Stereoisomerism; D013454:Sulfoxides / Q000138:chemical synthesis* / Q000737:chemistry
chemical_list: D000447:Aldehydes; D013454:Sulfoxides
keywords: -Thio; Additive Pummerer; Alkenyl sulfoxides; Alkynyl sulfoxides; Menthyl-p-toluenesulfinate