title: Highly stereoselective palladium-catalyzed dithiocarbonylation of propargylic mesylates with thiols and carbon monoxide.
abstract: Highly stereoselective dithiocarbonylation of propargylic mesylates with thiols and carbon monoxide has been developed by the use of tetrakis(triphenylphosphine)palladium(0) as the catalyst at 90 degrees C in THF. The reaction affords the corresponding dithioesters in good to excellent yields. For some secondary and tertiary propargylic alcohols with a terminal or internal triple bond, the reaction stereoselectively produces E-dithioesters as products. The dithiocarbonylation is believed to proceed via allenylpalladium and allenyl ester intermediates, and the high stereoselectivity might be rationalized by a mechanism where nucleophilic attack of a Pd(0)L(n) species on the allenyl sp carbon occurs from the less hindered side of an alkyl substituent.
authors.affiliation: Center for Catalysis Research and Innovation, Department of Chemistry, University of Ottawa, 10 Marie Curie, Ottawa, Ontario K1N 6N5, Canada. wxiao@mail.ccnu.edu.cn
authors.forename: Wen-Jing
authors.initials: WJ
authors.lastname: Xiao
authors.forename: Howard
authors.initials: H
authors.lastname: Alper
mesh_terms: D000480:Alkynes / Q000138:chemical synthesis* / Q000737:chemistry; D002248:Carbon Monoxide / Q000737:chemistry*; D002384:Catalysis; D008698:Mesylates / Q000138:chemical synthesis* / Q000737:chemistry; D015394:Molecular Structure; D010165:Palladium / Q000737:chemistry*; D013237:Stereoisomerism; D013438:Sulfhydryl Compounds / Q000737:chemistry*
chemical_list: D000480:Alkynes; D008698:Mesylates; D013438:Sulfhydryl Compounds; D010165:Palladium; D002248:Carbon Monoxide