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The mechanism of the Wittig reaction of anisaldehyde with a stabilized ylide was studied by a combination of (13)C kinetic isotope effects, conventional calculations, and molecular dynamics calculations in a cluster of 53 THF molecules. The isotope effects support a cycloaddition mechanism involving two sequential transition states associated with separate C-C and P-O bond formations. However, the betaine structure in between the two transition states is bypassed as an equilibrated intermediate in most trajectories. The role of the dynamics of solvent equilibration in the nature of mechanistic intermediates is discussed.

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Chen, Z.; Nieves-Quinones, Y.; Waas, J. R.; Singleton, D. A.  J. Am. Chem. Soc. 2014, 136, 13122-13125Contributed by Steven Bachrach.Reposted from Computational Organic Chemistry with permissionIf you hadnt noticed, I am a big fan of the work that Dan...
If you hadnt noticed, I am a big fan of the work that Dan Singleton is doing concerning the role of dynamics in discerning reaction mechanisms. Dans group has reported another outstanding study combining experiments, traditional QM computations, and molecular...