Issue 8, 2011
From the journal:

Organic & Biomolecular Chemistry

The SAMP alkylation: A computational study†‡

Rainer Koch*a  

* Corresponding authors

a Institut für Reine und Angewandte Chemie and Center of Interface Science, Carl von Ossietzky Universität Oldenburg, P.O. Box 2503, Oldenburg, Germany
E-mail: rainer.koch@uni-oldenburg.de
Fax: +49-441-798-193653
Tel: +49-441-798-3653

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

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Article information

DOI
https://doi.org/10.1039/C0OB01125H
Article type
Paper
Submitted
06 Dec 2010
Accepted
01 Feb 2011
First published
02 Feb 2011

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

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The SAMP alkylation: A computational study

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

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