Room temperature intramolecular hydro-O-alkylation of aldehydes: sp 3 C-H functionalization via a lewis acid catalyzed tandem 1,5-hydride transfer/cyclization

Organic Letters

Volumn 7, Issue 24, 2005, Pages 5429-5431

  Pastine, Stefan J ^a   Sames, Dalibor ^a  

^a Howard Hughes Medical Institute   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ALDEHYDE; DYES, REAGENTS, INDICATORS, MARKERS AND BUFFERS;

ALKYLATION; ARTICLE; CATALYSIS; CHEMICAL STRUCTURE; CHEMISTRY; CYCLIZATION; TEMPERATURE;

ALDEHYDES; ALKYLATION; CATALYSIS; CYCLIZATION; INDICATORS AND REAGENTS; MOLECULAR STRUCTURE; TEMPERATURE;

EID: 28844500714     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol0522283     Document Type: Article

References (16)

1. Pastine, S. J.; McQuaid, K. M.; Sames, D. J. Am. Chem. Soc. 2005, 127, 12180-12181.
2. Delongchamps, P. Organic Chemistry Series; Vol. 1: Steroelectronic Effects in Organic Chemistry; Baldwin, J. E., Ed.; Pergamon Press: Oxford, 1983; pp 5-20.
3. Woodward, R. B.; Sondheimer, F.; Mazur, Y. J. Am. Chem. Soc. 1958, 80, 6693-6694.
4. For reviews on the synthesis of spiroketals including spirioketal natural products, see: (a) Mead, K. T.; Brewer, B. N. Curr. Org. Chem. 2003, 7, 227-256.
5. (b) Perron, F.; Albizati, K. F. Chem. Rev. 1989, 89, 1617-1661.
6. (c) Boivin, T. L. B. Tetrahedron 1987, 43, 3309-3362.
7. C-H to C-O: Schulz, J. G. D.; Onopchenko, A. J. Org. Chem. 1978, 43, 339-340. Only two examples are provided in this report.
8. C-H to C-N: (a) Wölfling, J.; Frank, É.; Schneider, G.; Tietze, L. F. Angew. Chem., Int. Ed. 1998, 38, 200-201.
9. (b) Wölfling, J.; Frank, É.; Schneider, G.; Tietze, L. F. Eur. J. Org. Chem. 2004, 90-100.
10. 4.
11. For deuterium studies regarding the epimerization of spirostanols, see: Seo, S.; Uomori, A.; Takeda, K. J. Org. Chem. 1986, 51, 3823-3827.
12. DFT calculations were preformed using Jaguar 4.1. See Supporting Information for details.
13. Subjection of 21 to the reaction conditions yields the same ratio of 20:21.
14. The formation of 21 from 20 is essentially the reverse of the reactions in ref 4.
15. The opening of a spiroketal without substitution along the tether has been reported: Deslongchamps, P.; Rowan, D. D.; Potheir, N. Heterocycles 1981, 15, 1093-1096.
16. Aldol products were found to be the major products of these reactions.