Is the A-Ring of Sparteine Essential for High Enantioselectivity in the Asymmetric Lithiation−Substitution of N-Boc-pyrrolidine?

The simplest chiral portion of sparteine, N,N ‘-dimethyl-2-endo-methylbispidine, was prepared and evaluated in the asymmetric lithiation−substitution of N-Boc-pyrrolidine. The results indicate that the complete A-ring of sparteine is essential for high levels of asymmetric induction. DFT-QSSR analys...

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Bibliographic Details
Published in:Journal of the American Chemical Society 2004-12, Vol.126 (47), p.15473-15479
Main Authors: Phuan, Puay-Wah, Ianni, James C, Kozlowski, Marisa C
Format: Article
Language:English
Subjects:
Chemistry
Diamines - chemistry
Exact sciences and technology
Kinetics and mechanisms
Lithium - chemistry
Models, Molecular
Molecular Conformation
Organic chemistry
Organometallic Compounds - chemistry
Pyrrolidines - chemistry
Quantitative Structure-Activity Relationship
Reactivity and mechanisms
Sparteine - chemistry
Stereoisomerism
Thermodynamics
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Summary:The simplest chiral portion of sparteine, N,N ‘-dimethyl-2-endo-methylbispidine, was prepared and evaluated in the asymmetric lithiation−substitution of N-Boc-pyrrolidine. The results indicate that the complete A-ring of sparteine is essential for high levels of asymmetric induction. DFT-QSSR analyses of the diamine/Li+ complexes and DFT calculations of the pertinent i-PrLi/diamine/N-Boc-pyrrolidine complexes are predictive and provide complementary pictures of the stereochemical features critical to this transformation.
ISSN:0002-7863
1520-5126
DOI:10.1021/ja046321i