Issue 12, 2014

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

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

Associated articles

Supplementary files

Article information

Article type
Edge Article
Submitted
12 Jul 2014
Accepted
10 Aug 2014
First published
11 Aug 2014

Chem. Sci., 2014,5, 4975-4979

Author version available

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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