title: Steric effects compete with aryne distortion to control regioselectivities of nucleophilic additions to 3-silylarynes.
abstract: We report an experimental and computational study of 3-silylarynes. The addition of nucleophiles yield ortho-substituted products as a result of aryne distortion, but meta-substituted products form predominately when the nucleophile is large. Computations correctly predict the preferred site of attack observed in both nucleophilic addition and cycloaddition experiments. Nucleophilic additions to 3-tert-butylbenzyne, which is not significantly distorted, give meta-substituted products.
authors.affiliation: Department of Chemistry and Biochemistry, University of California, Los Angeles, California 90095, USA.
authors.forename: Sarah M
authors.initials: SM
authors.lastname: Bronner
authors.forename: Joel L
authors.initials: JL
authors.lastname: Mackey
authors.forename: K N
authors.initials: KN
authors.lastname: Houk
authors.forename: Neil K
authors.initials: NK
authors.lastname: Garg
mesh_terms: D001555:Benzene Derivatives / Q000737:chemistry*; D061565:Cycloaddition Reaction; D008958:Models, Molecular; D017646:Organosilicon Compounds / Q000737:chemistry*; D013237:Stereoisomerism
chemical_list: D001555:Benzene Derivatives; D017646:Organosilicon Compounds; C524146:benzyne