A Computational Study of the Copper(II)-Catalyzed Enantioselective Intramolecular Aminooxygenation of Alkenes

作者：Belding Lee; Chemler Sherry R; Dudding Travis^*

来源：Journal of Organic Chemistry, 2013, 78(20): 10288-10297.

DOI：10.1021/jo401665n

The origin of the enantioselectivity in the [Cu(R,R)-Ph-box](OTf)(2)-catalyzed intramolecular aminooxygenation of N-sulfony1-2-allylanilines and 4-pentenylsulfonamides to afford chiral indolines and pyrrolidines, respectively, was investigated using density functional theory (DFT) calculations. The pyrrolicline-forming transition-state model for the major enantiomer involves a chairlike seven-membered cydization 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.

• 出版日期2013-10-18