Issue 8, 2011

The SAMP alkylation: A computational study

Abstract

In a computational study of a stereoselective C–C bond formation, the SAMP alkylation, a previously proposed SE2′-front mechanism is evaluated taking into account all current experimental evidence. Using semiempirical, density functional and perturbation theoretical methods, the structure of the key intermediate is revealed and the metalloretentive nature of the mechanism is explained. The experimental ee values of a range of reactions with different electrophiles and carbonyl sources can be correlated with calculated differences in activation energies. Furthermore, it can be concluded that the selectivity derives from the internal stabilization of the transition state 3_syn (corresponding to an electrophilic attack from above the lithiohydrazone plane) by electrophile–lithium interactions. The fast computational approach can be used best as a screening method which excludes less promising candidates to guide this synthetic method.

Graphical abstract: The SAMP alkylation: A computational study

Supplementary files

Article information

Article type
Paper
Submitted
06 Dec 2010
Accepted
01 Feb 2011
First published
02 Feb 2011

Org. Biomol. Chem., 2011,9, 2885-2891

The SAMP alkylation: A computational study

R. Koch, Org. Biomol. Chem., 2011, 9, 2885 DOI: 10.1039/C0OB01125H

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