Journal
JOURNAL OF ORGANIC CHEMISTRY
Volume 78, Issue 20, Pages 10288-10297Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jo401665n
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Funding
- National Institutes of Health NIGMS [GM-078383]
- Queen Elizabeth II Scholarship
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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.
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