A density functional study of the relative stability of intermediates in a McMurry coupling reaction
The intramolecular McMurry reaction is a relatively common method for assembling carbocycles in organic synthesis. Most typically, this reaction involves a reductive coupling mediated by Ti(II). However, there are few examples of intramolecular McMurry reactions in the presence of Lewis basic heteroatoms. In this work, we investigate the titanium-mediated McMurry coupling leading to a pyrrolidine methoxy keto ester. Specifically, we compare the relative energies of all possible reaction intermediates at the B3LYP/6-31G level of theory. The most stable intermediate is found to be the one resulting from deoxygenation of the α-methoxy ketone. The McMurry product is not predicted to form.
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Livingston, A. J., Lindsay, H. A., & Milletti, M. C. (2012). A density functional study of the relative stability of intermediates in a McMurry coupling reaction. Journal of Coordination Chemistry, 65(9), 1484–1492. doi:10.1080/00958972.2012.674113