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Volumn 5, Issue 12, 1999, Pages 3464-3470

Experimental and theoretical investigations of lithio-indenyl carbamate/(-)-sparteine and (-)-α-isosparteine complexes

Author keywords

( ) Sparteine; Chiral carbanions; Line shape analysis; Lithiation; Semi empirical calculations

Indexed keywords

CARBAMIC ACID DERIVATIVE; SPARTEINE; SPARTEINE DERIVATIVE; UNCLASSIFIED DRUG;

EID: 0032793864     PISSN: 09476539     EISSN: None     Source Type: Journal    
DOI: 10.1002/(SICI)1521-3765(19991203)5:12<3464::AID-CHEM3464>3.0.CO;2-Q     Document Type: Article
Times cited : (32)

References (55)
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    • Beak and co-workers were able to enhance enantioselectivity with a kinetic resolution by trapping preferentially the more reactive diastereomer of the epimeric lithio N-pivaloyl-o-ethylaniline/(-)-sparteine complexes with 0.45 equiv of trimethylsilyl chloride, while the remaining diastereomer epimerized by warming the reaction mixture to -25°C and by addition of another 0.45 equiv trimethylsilyl chloride; A. Basu, J. Gallagher, P. Beak, J. Org. Chem. 1996, 61, 5718-5719.
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    • note
    • E′ mechanism as it was found for other allyllithium sparteine complexes.[refs. 4d, 7c, 12] The low enantioenrichment in the products kept us from continuing our efforts in structure elucidation of silanes 7a and 7b.
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    • note
    • Semiempirical calculations (MOPAC, PM3) give 5% longer C-Li and C-N-bonds for (-)-α-isosparteine/mdenide-complexes 6 compared with (-)-sparteine-complexes 5.
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    • 2-symmetry of (-)-sparteine, should be transferable to the transition state of the lithiation.
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    • note
    • E′-mechanism, no interaction between the electrophiles methyl iodide and trimethylsilyl chloride should exist and the configuration of the lithium should have no influence on the enantioenrichment in the substitution products. This configuration could have an influence in the reaction with carbonyl compounds, though, were a precoordination between the lithium and the carbonyl oxygen is supposed [ref. 2a].
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