title: A computational study of the copper(II)-catalyzed enantioselective intramolecular aminooxygenation of alkenes.
abstract: The origin of the enantioselectivity in the [Cu(R,R)-Ph-box](OTf)2-catalyzed intramolecular aminooxygenation of N-sulfonyl-2-allylanilines and 4-pentenylsulfonamides to afford chiral indolines and pyrrolidines, respectively, was investigated using density functional theory (DFT) calculations. The pyrrolidine-forming transition-state model for the major enantiomer involves a chairlike seven-membered cyclization transition state with a distorted square-planar copper center, while the transition-state model for the minor enantiomer was found to have a boatlike cyclization geometry having a distorted tetrahedral geometry about the copper center. Similar copper-geometry trends were observed in the chiral indoline-forming reactions. These models were found to be qualitatively consistent with experimental results and allow for rationalization of how substitution on the substrate backbone and N-sulfonyl substituent affect the level of enantioselectivity in these and related copper(II)-catalyzed enantioselective reactions.
authors.affiliation: Department of Chemistry, Brock University , St. Catharines, Ontario, Canada L2S 3A1.
authors.forename: Lee
authors.initials: L
authors.lastname: Belding
authors.forename: Sherry R
authors.initials: SR
authors.lastname: Chemler
authors.forename: Travis
authors.initials: T
authors.lastname: Dudding
mesh_terms: D000475:Alkenes / Q000737:chemistry*; D000814:Aniline Compounds / Q000737:chemistry; D002384:Catalysis; D003300:Copper / Q000737:chemistry; D003500:Cyclization; D007211:Indoles / Q000737:chemistry*; D015394:Molecular Structure; D013237:Stereoisomerism; D013438:Sulfhydryl Compounds / Q000737:chemistry
chemical_list: D000475:Alkenes; D000814:Aniline Compounds; D007211:Indoles; D013438:Sulfhydryl Compounds; C057812:indoline; D003300:Copper
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