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Issue 12, 2014
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Electrostatic control of regioselectivity via ion pairing in a Au(I)-catalyzed rearrangement

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Abstract

The rearrangement of 3-substituted aryl alkynyl sulfoxides catalyzed by cationic Au(I) complexes was studied with different counterions in solvents spanning a range of dielectric constants (ε). Pulsed-gradient diffusion NMR experiments demonstrated strong ion pairing in low-ε solvents. The regioselectivity of the reaction was insensitive to ε when ion pairing was weak but increased monotonically as ε was decreased in the regime of strong ion pairing. DFT calculations of putative product-determining transition states indicated that the product resulting from the more polar transition state is favored due to electrostatic stabilization in the presence of strong ion pairing.

Graphical abstract: Electrostatic control of regioselectivity via ion pairing in a Au(i)-catalyzed rearrangement

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Publication details

The article was received on 12 Jul 2014, accepted on 10 Aug 2014 and first published on 11 Aug 2014


Article type: Edge Article
DOI: 10.1039/C4SC02058H
Author version available: Download Author version (PDF)
Citation: Chem. Sci., 2014,5, 4975-4979
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    Electrostatic control of regioselectivity via ion pairing in a Au(I)-catalyzed rearrangement

    V. M. Lau, C. F. Gorin and M. W. Kanan, Chem. Sci., 2014, 5, 4975
    DOI: 10.1039/C4SC02058H

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