An efficient and stereoselective synthesis of enantiopure 1,2,7- trihydroxylated pyrrolizidines

Tetrahedron Letters

Volumn 40, Issue 33, 1999, Pages 6083-6086

  De Vicente, Javier ^a   Arrayás, Ramón Gómez ^a   Carretero, Juan C ^a  

^a UNIVERSIDAD AUTÓNOMA DE MADRID   (Spain)

Author keywords

, unsaturated sulfones; Lipases; Pyrrolizidines; Stereoselective synthesis

Indexed keywords

PYRROLIZIDINE DERIVATIVE; SULFONE DERIVATIVE;

ARTICLE; CHEMICAL REACTION; CHEMICAL STRUCTURE; CONFORMATIONAL TRANSITION; CYCLIZATION; DEACETYLATION; HYDROLYSIS; ISOMERISM; REACTION ANALYSIS; STEREOCHEMISTRY; SYNTHESIS;

EID: 0033551798     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4039(99)01265-4     Document Type: Article

References (25)

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3. Recent reviews: a) Liddell, J. R. Nat. Prod. Rep. 1998, 15, 363.
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7. See, also: Dai, W.-M.; Nagao, Y. Heterocycles 1990, 30, 1231.
8. a) Casuarine isolation: Nash, R. J.; Thomas, P. I.; Waigh, R. D.; Fleet, G. W. J.; Wormald, M. R.; de Q. Lilley, P. M.; Watkin, D. J. Tetrahedron Lett. 1994, 35, 7849.
9. b) Alexine isolation: Nash, R. J.; Fellows, L. E.; Dring, J. V.; Fleet, G. W. J.; Derome, A. E.; Hamor, T. A.; Scofield, A. M.; Watkin, D. J. Tetrahedron Lett. 1988, 29, 2487.
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11. For recent syntheses of alexines and related pyrrolizidines, see: a) Denmark, S. E.; Martinborough, E. A. J. Am. Chem. Soc. 1999, 121, 3046.
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19. Carretero, J. C.; Gómez Arrayás, R. J. Org. Chem. 1998, 63, 2993.
20. Carretero, J. C.; Domínguez, E. J. Org. Chem. 1992, 57, 3867.
21. Daicel Chiracel OD column; eluting with hexane/i-PrOH mixture, 90:10 v/v, 1.0 ml/min; retention times of 19 min and 24 min for (S)-2a and (R)-2a, respectively.
22. A similar dependence of the stereoselectivity of the cyclization with the nature and size of the protecting group at γ position had been observed from similar ω-nitrogenated-γ-oxygenated-α,β-unsaturated sulfones. See: Carretero, J. C.; Gómez Arrayás, R; Storch de Gracia, I. Tetrahedron Lett. 1996, 37, 3379.
23. The stereochemical assignment of the pyrrolizidines 7, 8, 12 and 11 (obtained by acetylation of 10) was established mainly by analysis of their NOESY experiments (figures below) and by comparison with the stereochemical behaviour of related indolizidines (reference 5). For the use of the coupling constants in the configurational assignment of alexine stereoisomers, see: Wormald, M. R.; Nash, R. J.; Hrnciar, P.; White, J. D.; Molyneux, R. J.; Fleet, G. W. J. Tetrahedron: Asymmetry 1998, 9, 2549.
24. (equation presented)
25. D = -29.3 (c 0.15, MeOH), see: Carpenter, N. M.; Fleet, G. W. J.; Bello I. C.; Winchester, B.; Fellows, L. E.; Nash, R. J. Tetrahedron Lett. 1989, 30, 7261.