Transannular 1,5-hydride shift in 5-hydroxycyclooctanone: an experimental and theoretical investigation?
Organic & Biomolecular Chemistry Pub Date: 2007-07-12 DOI: 10.1039/B708448J
Abstract
1 H NMR measurements have shown that eight out of twelve methylene hydrogen atoms of 5-hydroxycyclooctanone (1HK) are exchanged for deuterium atoms under acidic and basic conditions. For the reaction in 7.9 M DCl/D2O, an activation energy Ea = 19.2 ± 0.4 kcal mol?1 is found. In order to explain these findings, a degenerate transannular 1,5-hydride shift is essential, and this reaction has been analyzed by quantum chemical calculations. Hydride transfer takes place via a tight transition state with a six-membered ring. The activation barrier is lowest in the presence of base. The molecular conformation of the eight-membered ring in the transition state resembles that of the starting structure. It is unlikely that solvent molecules such as water participate in the formation of the transition state.
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Journal Name：Organic & Biomolecular Chemistry
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CAS no.: 89640-58-4
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