The cyclopropylmethylsilane terminated Prins reaction: Stereoelectronic controlled formation of (E)-skipped dienes alcohols and a (Z)-skipped diene modification

Synlett

Volumn , Issue 3, 2003, Pages 345-348

  Braddock, D Christopher ^a   Badine, D Michael ^a   Gottschalk, Thomas ^a   Matsuno, Ai ^a   Rodriguez Lens, Margarita ^a  

^a IMPERIAL COLLEGE LONDON   (United Kingdom)

Author keywords

Buttressing; Cyclopropylmethyl cation; Prins; Skipped dienes; Stereoelectronic

Indexed keywords

1 PHENYLDIMETHYLSILYL 2 VINYLCYCLOPROPANE; ALCOHOL DERIVATIVE; ALDEHYDE; ALKENE; ALUMINUM DERIVATIVE; CYCLOPROPANE DERIVATIVE; UNCLASSIFIED DRUG;

ARTICLE; CARBON NUCLEAR MAGNETIC RESONANCE; CHEMICAL MODIFICATION; CHEMICAL REACTION; GEOMETRY; PRINS REACTION;

EID: 0037288293     PISSN: 09365214     EISSN: None     Source Type: Journal    
DOI: 10.1055/s-2003-37111     Document Type: Article

References (18)

1. Snider, B. B. In Comprehensive Organic Synthesis, Vol. 2; Trost, B. M.; Fleming, I., Eds.; Pergamon Press: Oxford, 1991, 527.
2. For the 'pinacol-terminated Prins reaction' and its application for the preparation of multifunctional tetrahydrofurans see: Hanaki, N.; Link, J. T.; MacMillan, D. W. C.; Overman, L. E.; Trankle, W. G.; Wurster, J. A. Org. Lett. 2000, 2, 223; and references cited therein.
3. Hosomi, A.; Sakurai, H. Tetrahedron Lett. 1976, 16, 1295.
4. Snider, B. B. Acc. Chem. Res. 1980, 13, 426.
5. Danishefsky, S. J. Aldrichimica Acta 1986, 19, 59.
6. Braddock, D. C.; Badine, D. M.; Gottschalk, T. Synlett 2001, 1909.
7. (a) Pittman, C. U. Jr.; Olah, G. A. J. Am. Chem. Soc. 1965, 87, 5123.
8. -1 more stable than the perpendicular conformation: Kabakoff, D. S.; Nanamworth, E. J. Am. Chem. Soc. 1970, 92, 3234.
9. 2-petroleum ether 40-60 °C) to give the skipped diene alcohol product.
10. Data for compounds 5a-k. Diene 5a: Colourless oil. IR (thin film): Abstract
11. Martin, M. Synth. Commun. 1983, 13, 809.
12. 4. For an example see: Wilson, S. R.; Zucker, P. A. J. Org. Chem. 1988, 53, 4682.
13. 2: C, 64.61; H, 9.04. Found: C, 64.53; H, 8.93.
14. Irradiation of the TMS group in alcohol 12a results in enhancements for two cyclopropyl protons. For alcohol 12b only one cyclopropyl proton is enhanced. Relative to the TMS group, this unambiguously places the pendant phenyldimethylsilylmethyl group trans for the former and cis for the latter.
15. Dess, D. B.; Martin, J. C. J. Am. Chem. Soc. 1991, 113, 7277.
16. +, 289.1807.
17. (a) The diene isomers were assigned by the NMR method of Chan et. al.: Chan, T. H.; Mychajlowskij, W.; Amouroux, R. Tetrahedron Lett. 1977, 19, 1605.
18. 13C resonance for the TMS group at -1.20 ppm. Skipped diene (Z)-15 displays its equivalent resonance at 0.41 ppm.