Single-Isomer Tetrasubstituted Olefins from Regioselective and Stereospecific Palladium-Catalyzed Coupling of β-Chloro-α-iodo-α,β-unsaturated Esters

• Published in: Journal of organic chemistry Vol. 71; no. 9; pp. 3615 - 3618
• Main Authors: Lemay, Alison B, Vulic, Katarina S, Ogilvie, William W
• Format: Journal Article
• Language: English
• Published: WASHINGTON American Chemical Society 28.04.2006; Amer Chemical Soc
• Subjects: Alkenes - chemical synthesis; Catalysis; Chemistry; Chemistry, Organic; Esters; Exact sciences and technology; Hydrocarbons, Chlorinated - chemistry; Hydrocarbons, Iodinated - chemistry; Organic chemistry; Palladium - chemistry; Physical Sciences; Science & Technology; Stereoisomerism; HALIDES; ALKENES; SUZUKI; ROUTE; FACILE SYNTHESIS; IODINE MONOCHLORIDE; STEREOSELECTIVE-SYNTHESIS; INTERNAL ALKYNES; EFFICIENT; ARYLBORONIC ACIDS; Catalytic reaction; Transition element complexes; Acetylenic compound; Regioselectivity; Palladium complex; Selectivity; Organic chlorine compounds; Chemical coupling; Unsaturated compound; Stereoselectivity; Ester; Organic iodine compounds; Olefin; Stereospecificity; Platinoid Complexes; Chemical reactivity; Chemical synthesis; Ethylenic compound
• ISSN: 0022-3263; 1520-6904
• DOI: 10.1021/jo060144h

The efficient regioselective and stereospecific synthesis of tetrasubstituted olefins using a mild and convenient method is disclosed. 2-Alkynyl esters are selectively converted to E-β-chloro-α-iodo-α,β-unsaturated esters by exposure to Bu4NI in refluxing dichloroethane. These products are produced cleanly, regio- and stereoselectively, and in high yields. Single-isomer tetrasubstituted olefins bearing four different carbon substituents are then synthesized by sequential palladium-catalyzed coupling reactions. Selectivity results from reactivity differences in the intermediate substrates.