Intramolecular 1,5- versus 1,6-Hydrogen Abstraction Reaction Promoted by Alkoxy Radicals in Carbohydrate Models

Organic Letters

Volumn 4, Issue 11, 2002, Pages 1959-1961

  Francisco, Cosme G ^a   Freire, Raimundo ^a   Herrera, Antonio J ^a   Peréz Martín, Inés ^a   Suárez, Ernesto ^a  

^a INSTITUTO DE PRODUCTOS NATURALES Y AGROBIOLOGÍA   (Spain)

Author keywords

[No Author keywords available]

Indexed keywords

CARBOHYDRATE; DYES, REAGENTS, INDICATORS, MARKERS AND BUFFERS; FREE RADICAL; HYDROGEN;

ARTICLE; CHEMICAL STRUCTURE; CHEMISTRY;

CARBOHYDRATES; FREE RADICALS; HYDROGEN; INDICATORS AND REAGENTS; MODELS, MOLECULAR;

EID: 0037198775     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol025981u     Document Type: Article

References (36)

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2. Recent reviews: (a) Majetich, G. Tetrahedron 1995, 51, 7095-7129. (b) Feray, L.; Kuznetsov, N.; Renaud P. In Radicals in Organic Synthesis; Renaud, P., Sibi, M. P., Eds.; Wiley-VCH: Weinheim, 2001; Vol. 2, pp 246-278. (c) Robertson, J.; Pillai, J.; Lush, R. K. Chem. Soc. Rev. 2001, 30, 94-103.
3. Recent reviews: (a) Majetich, G. Tetrahedron 1995, 51, 7095-7129. (b) Feray, L.; Kuznetsov, N.; Renaud P. In Radicals in Organic Synthesis; Renaud, P., Sibi, M. P., Eds.; Wiley-VCH: Weinheim, 2001; Vol. 2, pp 246-278. (c) Robertson, J.; Pillai, J.; Lush, R. K. Chem. Soc. Rev. 2001, 30, 94-103.
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11. HAT reaction through eight-membered transition states or higher promoted by alkoxy radicals which suffer a severe entropie penalty are practically unknown. Recently an IHA through a nine-membered transition state between glucopyranose units in a disaccharide model has been observed in this laboratory: Francisco, C. G.; Herrera, A. J.; Kennedy, A. R.; Melián, D.; Suárez, E. Angew. Chem., Int. Ed. . 2002, 41, 860-862.
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21. An example of the influence of the substituents in the 1,5-HAT reaction compared with competing β-fragmentation of alkoxy radicals has been published: Allen, P. R.; Brimble, M. A.; Farès, F. A. J. Chem. Soc., Perkin Trans. 1 1998, 2403-2411.
22. No products arising from the geometrically possible abstraction of the hydrogen at C5 have been detected in the examples described in this Letter. Probably the abstraction at C7 is favored by steric and stereoelectronic factors. For studies on stereoelectronic effects in intermolecular hydrogen abstraction reactions, see: (a) Malatesta, V.; Ingold, K. U. J. Am. Chem. Soc. 1981, 103, 609-614. (b) Beckwith, A. L. J.; Easton, C. J. J. Am. Chem. Soc. 1981, 103, 615-619.
23. No products arising from the geometrically possible abstraction of the hydrogen at C5 have been detected in the examples described in this Letter. Probably the abstraction at C7 is favored by steric and stereoelectronic factors. For studies on stereoelectronic effects in intermolecular hydrogen abstraction reactions, see: (a) Malatesta, V.; Ingold, K. U. J. Am. Chem. Soc. 1981, 103, 609-614. (b) Beckwith, A. L. J.; Easton, C. J. J. Am. Chem. Soc. 1981, 103, 615-619.
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30. For studies of the influence of polar factors on the intermolecular hydrogen abstraction reactions, see: (a) Beckwith, A. L. J.; Zavitsas, A. A. J. Am. Chem. Soc. 1995, 117, 607-614. (b) Zavitsas, A. A.; Chatgilialoglu, C. J. Am. Chem. Soc. 1995, 117, 10645-10654. (c) Kaushal, P.; Mok, P. L. H.; Roberts, B. P. J. Chem. Soc., Perkin Trans. 2 1990, 1663-1670. For an example of correlation between proximity in the ground state and regioselectivity in an IHA reaction, see ref 2c.
31. For studies of the influence of polar factors on the intermolecular hydrogen abstraction reactions, see: (a) Beckwith, A. L. J.; Zavitsas, A. A. J. Am. Chem. Soc. 1995, 117, 607-614. (b) Zavitsas, A. A.; Chatgilialoglu, C. J. Am. Chem. Soc. 1995, 117, 10645-10654. (c) Kaushal, P.; Mok, P. L. H.; Roberts, B. P. J. Chem. Soc., Perkin Trans. 2 1990, 1663-1670. For an example of correlation between proximity in the ground state and regioselectivity in an IHA reaction, see ref 2c.
32. For studies of the influence of polar factors on the intermolecular hydrogen abstraction reactions, see: (a) Beckwith, A. L. J.; Zavitsas, A. A. J. Am. Chem. Soc. 1995, 117, 607-614. (b) Zavitsas, A. A.; Chatgilialoglu, C. J. Am. Chem. Soc. 1995, 117, 10645-10654. (c) Kaushal, P.; Mok, P. L. H.; Roberts, B. P. J. Chem. Soc., Perkin Trans. 2 1990, 1663-1670. For an example of correlation between proximity in the ground state and regioselectivity in an IHA reaction, see ref 2c.
33. Evidence for a deactivating influence of a β-oxygen in the intermolecular hydrogen abstraction reaction has been described: (a) Busfield, W. K.; Grice, I. D.; Jenkins, I. D.; Monteiro, M. J. J. Chem. Soc., Perkin Trans. 2 1994, 1071-1077. (b) Busfield, W. K.; Grice, I. D.; Jenkins, I. D. J. Chem. Soc., Perkin Trans. 2 1994, 1079-1086.
34. Evidence for a deactivating influence of a β-oxygen in the intermolecular hydrogen abstraction reaction has been described: (a) Busfield, W. K.; Grice, I. D.; Jenkins, I. D.; Monteiro, M. J. J. Chem. Soc., Perkin Trans. 2 1994, 1071-1077. (b) Busfield, W. K.; Grice, I. D.; Jenkins, I. D. J. Chem. Soc., Perkin Trans. 2 1994, 1079-1086.
35. Bicyclic ketals can be easily converted into the corresponding bicyclic ethers by stereoselective reduction: (a) Takemoto, Y.; Furuse, S.-i.; Hayase, H.; Echigo, T.; Iwata, C.; Tanaka, T.; Ibuka, T. Chem. Commun. 1999, 2515-2516. (b) Nicolaou, K. C.; Hwang, C.-K.; Nugiel, D. A. J. Am. Chem. Soc. 1989, 111, 4136-4137
36. Bicyclic ketals can be easily converted into the corresponding bicyclic ethers by stereoselective reduction: (a) Takemoto, Y.; Furuse, S.-i.; Hayase, H.; Echigo, T.; Iwata, C.; Tanaka, T.; Ibuka, T. Chem. Commun. 1999, 2515-2516. (b) Nicolaou, K. C.; Hwang, C.-K.; Nugiel, D. A. J. Am. Chem. Soc. 1989, 111, 4136-4137