title: Regioselectivity in the intramolecular Heck reaction of a series of cyclic sulfonamides: an experimental and computational study.
abstract: Regioselectivity in the intramolecular Heck reaction of a series of N-sulfonyl-2,5-dihydro-3-substituted pyrroles was studied. These substrates are unbiased in terms of the formed ring size of the new heterocycle. Results indicate that high levels of regioselectivity are observed under a range of conditions, and that there is an underlying propensity for carbon-carbon bond formation at the most hindered end of the alkene. For two examples (3-Me and 3-tBu), DFT calculations were performed and indicate that in both cases, the modelled transition state for carbopalladation is energetically lower for the experimentally preferred isomer.
authors.affiliation: Centre for Synthesis and Chemical Biology, School of Chemistry and Chemical Biology, University College Dublin, Dublin 4, Ireland.
authors.forename: Kimberly
authors.initials: K
authors.lastname: Geoghegan
authors.forename: Paul
authors.initials: P
authors.lastname: Evans
authors.forename: Isabel
authors.initials: I
authors.lastname: Rozas
authors.forename: Ibon
authors.initials: I
authors.lastname: Alkorta
mesh_terms: D000475:Alkenes / Q000737:chemistry; D002384:Catalysis; D018360:Crystallography, X-Ray; D003500:Cyclization; D008956:Models, Chemical; D008968:Molecular Conformation; D010165:Palladium / Q000737:chemistry; D011758:Pyrroles / Q000737:chemistry; D013237:Stereoisomerism; D013449:Sulfonamides / Q000737:chemistry*
chemical_list: D000475:Alkenes; D011758:Pyrroles; D013449:Sulfonamides; D010165:Palladium