Addition of a chiral boron enolate to cyclic N-acyliminium ions. Stereocontrolled synthesis of the pyrrolizidine ring system

Journal of Organic Chemistry

Volumn 61, Issue 9, 1996, Pages 3187-3190

  Pilli, Ronaldo A ^a   Russowsky, Dennis ^a  

^a UNIVERSITY OF CAMPINAS   (Brazil)

Author keywords

[No Author keywords available]

Indexed keywords

PYRROLIZINE DERIVATIVE;

ARTICLE; DRUG SYNTHESIS; NUCLEAR MAGNETIC RESONANCE; REACTION ANALYSIS; STEREOCHEMISTRY;

EID: 0029981020     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo9513020     Document Type: Article

References (32)

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4. For total synthesis of (+)- and (-)-hastanecine (1a), see: (a) Aasen, A. J.; Culvenor, C. C. J.; Smith, L. W. J. Org. Chem. 1969 34, 4137. (b) Hart, D. J.; Yang, T-K. J. Chem. Soc., Chem. Commun. 1983, 135. (c) Chamberlin, A. R.; Chung, J. Y. L. J. Org. Chem. 1985, 50, 4426. (d) Mulzer, J.; Scharp, M. Synthesis 1993, 615. For total synthesis of (+)-dihydroxyheliotridane (1b) see, ref 3d.
5. For total synthesis of (+)- and (-)-hastanecine (1a), see: (a) Aasen, A. J.; Culvenor, C. C. J.; Smith, L. W. J. Org. Chem. 1969 34, 4137. (b) Hart, D. J.; Yang, T-K. J. Chem. Soc., Chem. Commun. 1983, 135. (c) Chamberlin, A. R.; Chung, J. Y. L. J. Org. Chem. 1985, 50, 4426. (d) Mulzer, J.; Scharp, M. Synthesis 1993, 615. For total synthesis of (+)-dihydroxyheliotridane (1b) see, ref 3d.
6. For total synthesis of (+)- and (-)-hastanecine (1a), see: (a) Aasen, A. J.; Culvenor, C. C. J.; Smith, L. W. J. Org. Chem. 1969 34, 4137. (b) Hart, D. J.; Yang, T-K. J. Chem. Soc., Chem. Commun. 1983, 135. (c) Chamberlin, A. R.; Chung, J. Y. L. J. Org. Chem. 1985, 50, 4426. (d) Mulzer, J.; Scharp, M. Synthesis 1993, 615. For total synthesis of (+)-dihydroxyheliotridane (1b) see, ref 3d.
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13. -1 more stable than the one involved in the approach to the si face.
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17. The composition of the mixture 6a/6b proved to be of no consequence to the stereochemical outcome of the nueleophilic addition. The same product distribution was observed when either a 1:1 or a 19:1 mixture of 6a/6b was employed.
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28. 2BOTf was prepared according to ref 12b and freshly distilled before use.
29. Reaction of the boron enolate from (+)-7c and racemic 4 was carried out under the same conditions described above to afford a 1:1 mixture of two stereoisomers: 2c as the slow eluting isomer, and a fast eluting isomer to which structure i was tentatively assigned. (Equation Presented)
30. For a general experimental information see ref 10b.
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