Modeling and Experiment Reveal an Unexpected Stereoelectronic Effect on Conformation and Scalar Couplings of α-Aminoorganostannanes, with Possible Relevance to the Tin−Lithium Exchange Reaction

The solution conformation of N-methyl-2-(tributylstannyl)piperidines has been determined through the use of vicinal 119Sn−13C coupling constants, revealing a conformational distortion caused by an unexpected stereoelectronic effect in some cases. Specifically, the “equatorial” conformer is distorted...

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Bibliographic Details
Published in:Journal of organic chemistry 2003-10, Vol.68 (22), p.8480-8484
Main Authors: Santiago, Marcelina, Low, Eddy, Chambournier, Gilles, Gawley, Robert E
Format: Article
Language:English
Subjects:
Carbon Isotopes
Lithium - chemistry
Models, Chemical
Molecular Conformation
Nitrogen - chemistry
Nitrogen Isotopes
Organotin Compounds - chemistry
Piperidines - chemistry
Tin - chemistry
Trialkyltin Compounds - chemistry
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Summary:The solution conformation of N-methyl-2-(tributylstannyl)piperidines has been determined through the use of vicinal 119Sn−13C coupling constants, revealing a conformational distortion caused by an unexpected stereoelectronic effect in some cases. Specifically, the “equatorial” conformer is distorted into a half-chair, in which the nitrogen lone pair eclipses the C−Sn bond. This distortion, which “costs” approximately 1 kcal/mol, correlates with a conformational dependence of geminal 119Sn−15N couplings and a possible correlation with reactivity in the tin−lithium exchange reaction.
ISSN:0022-3263
1520-6904
DOI:10.1021/jo034948y