Iron(III)-catalyzed Prins-type cyclization using homopropargylic alcohol: A method for the synthesis of 2-alkyl-4-halo-5,6-dihydro-2H-pyrans

Organic Letters

Volumn 5, Issue 11, 2003, Pages 1979-1982

  Miranda, Pedro O ^a,b   Díaz, David D ^a,b   Padrón, Juan I ^a,b   Bermejo, Jaime ^a,b   Martín, Victor S ^a,b  

^a UNIVERSIDAD DE LA LAGUNA   (Spain)

^b INSTITUTO DE PRODUCTOS NATURALES Y AGROBIOLOGÍA   (Spain)

Author keywords

[No Author keywords available]

Indexed keywords

ALCOHOL DERIVATIVE; ALDEHYDE; FERRIC ION; PYRAN DERIVATIVE;

ARTICLE; CATALYSIS; CYCLIZATION; ISOLATION PROCEDURE; SYNTHESIS;

EID: 0141629466     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol034568z     Document Type: Article

References (38)

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25. 3 were purchased from the Aldrich Chemical Co.
26. Stereochemistry was determined by NOE studies. See Supporting Information
27. To the best of our knowledge, this is the first report on the use of Fe(III) halides promoting the Prins reaction.
28. For a coupling of homopropargylic alcohol with aldehydes yielding allylic alcohols, see: Takai, K.; Sakamoto, S. Isshiki, T. Org. Lett. 2003, 5, 653-655.
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30. For precedents in the synthesis of halovinyl tetrahydropyrans, see: (a) Melany, M. L.; Lock, G. A.; Thompson, D. W. J. Org. Chem. 1985, 50, 3925-3927. (b) Chan, T. H.; Arya, P. Tetrahedron Lett. 1989, 30, 4065-4068. (c) Tsukayama, M.; Utsumi, H.; Kunugi, A.; Nozaki, H. Heterocycles 1997, 45, 1131-1142.
31. For precedents in the synthesis of halovinyl tetrahydropyrans, see: (a) Melany, M. L.; Lock, G. A.; Thompson, D. W. J. Org. Chem. 1985, 50, 3925-3927. (b) Chan, T. H.; Arya, P. Tetrahedron Lett. 1989, 30, 4065-4068. (c) Tsukayama, M.; Utsumi, H.; Kunugi, A.; Nozaki, H. Heterocycles 1997, 45, 1131-1142.
32. 2. The combined organic layers were dried over magnesium sulfate, and the solvent was removed under reduced pressure. This crude reaction mixture was purified by flash silica gel column chromatography (n-hexane/EtOAc solvent systems).
33. 13C NMR). See Supporting Information.
34. For a precedent about the halogen transfer from halogenated solvents to a metal, see: Fürstner, A.; Mathes, C.; Lehmann, C. W. Chem. Eur. J. 2001, 7, 5299-5317.
35. This alternative could explain why the halide exchange does not occur in the homoallylic alcohols (Table 1).
36. At the moment, we cannot determine the fate of the remainder of the matter.
37. Reaction has been scaled up to 5 g with no difficulty.
38. 2 produces a 7:3 mixture of bromo and chloro dihydropyran derivatives.