Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 132, Issue 32, Pages 11071-11082Publisher
AMER CHEMICAL SOC
DOI: 10.1021/ja101104q
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Funding
- National Science Foundation [CHE09-56776]
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Distinguishing between the concerted second-order mechanism for beta-eliminations and nonconcerted mechanisms with discrete carbanion intermediates is very difficult experimentally, but the ability of quantum chemistry to find stationary points of the free-energy surface in liquid-phase solutions, even for complex reagents, provides a new tool for elucidating such mechanisms. Here we use liquid-phase density functional theory calculations to find transition states and intermediates on the free-energy surfaces of four base-initiated alpha,beta-eliminations of acetoxy and mesyloxy esters and their analogous thioesters. The geometries, free energies, and charge distributions of these structures support a stepwise irreversible first-order elimination from a conjugate base (E1cB(I)) mechanism with acetoxy ester 3, acetoxy thioester 4, and mesyloxy thioester 6. However, mesyloxy ester 5, which has an excellent nucleofuge and a less-acidic proton, follows a concerted but asynchronous E2 mechanism with an E1cB-like transition state. The anti transition state is more favorable than the syn one, even for the poorer nucleofuge and more-acidic thioesters. The article includes a general scheme for describing liquid-phase reactions in terms of free-energy surfaces.
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