A polymer-supported silyl triflate and subsequent functionalization: Synthesis and solid-phase Diels-Alder reactions of silyloxydienes

Tetrahedron Letters

Volumn 40, Issue 17, 1999, Pages 3285-3288

  Smith, Eric M ^a  

^a DUPONT COMPANY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ALKADIENE; POLYMER; SILANE DERIVATIVE; SILYLOXYDIENE; SILYLTRIFLATE; UNCLASSIFIED DRUG;

ARTICLE; CARBON NUCLEAR MAGNETIC RESONANCE; CHEMICAL BOND; PROTON NUCLEAR MAGNETIC RESONANCE; REACTION ANALYSIS; SOLID PHASE EXTRACTION; STRUCTURE ANALYSIS; SYNTHESIS;

EID: 0033597375     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4039(99)00440-2     Document Type: Article

References (20)

1. 1. For comprehensive lists of reactions adapted for solid-phase chemistry see: (a) The Combinatorial Index, Academic Press, San Diego, 1998.
2. (b) also see from Nova Biochem: The Combinatorial Chemistry Catalog, 1998.
3. 2. Fringuelli, F.; Taticchi, A. Dienes in the Diels-Alder Reaction, Wiley, New York, 1990.
4. 3. (a) Winkler, J. D.; McCoull, W. Tetrahedron Lett. 1998, 39, 4935.
5. (b) Wendeborn, S.; DeMesmaker, A.; Brill, W.K.-D.
6. (c) Crawshaw, M.; Hird, N.W.; Irie, K.; Nagai, K. Tetrahedron, Lett. 1997, 40, 7115.
7. (d) Tietze, L. F.; Hippe, T.; Steinmetz, A. Synlett 1996, 1044.
8. (e) Schlessinger, R. H.; Bergstrom, C. P. Tetrahedron Lett. 1996, 37, 2133.
9. (f) Yedida, V.; Leznoff, C. Can. J. Chem. 1980, 58, 1144.
10. (g) Gaviña, F.; Gil, P.; Palazón, B. Tetrahedron Lett. 1979, 15, 1333.
11. 4. Hu, Y.; Porco, J. A., Jr.; Labadie, J. W.; Gooding, O. W.; Trost., B. M. J. Org. Chem. 1998, 63, 4518.
12. 5. (a) Danishefsky, S.; Kitahara, T. J. Am. Chem. Soc. 1974, 96, 7807.
13. (b) Danishefsky, S.; Kitahara, T.; Yan, C. F.; Morris, J. J. Am. Chem. Soc. 1979, 101, 6996.
14. 6. A typical procedure for synthesizing the PS-DES triflate is as follows: Under an inert atmosphere, PS-DES resin (500 mg, 0.36 mmol based on loading of 0.72 mmol/g) was washed with three 10-mL portions of methylene chloride. To the resin was then added 5 mL of methylene chloride, and then a solution of trifluoromethanesulfonic acid (96 μL, 1.08 mmol) in 5 mL methylene chloride. After shaking five minutes, the solution was drained, and the resin was washed with three 10-mL portions of methylene chloride to afford a bright orange resin.
15. 7. Svensson, A.; Fex, T.; Kihlberg, J. Tetrahedron Lett. 1996, 37, 7649.
16. 8. A typical procedure for the derivitization of PS-DES triflate is as follows: To PS-DES triflate resin (0.358 mmol) was added 5 mL of methylene chloride and then a solution of diisopropylethylamine (0.19 mL, 1.07 mmol) and 3,4-dimethoxybenzylideneacetone (0.081g, 0.394 mmol) in 5 mL methylene chloride. After shaking 10 min., the solution was drained, and the resin was washed with three 10-mL portions of methylene chloride to afford 4 as a light tan resin.
17. 9. When derivitizing the triflate resin with ketones such as 2-cyclohexenone, where two, competing acidic protons are present, the reaction is not regioselective, and a mixture of 1-and 2-silyloxy-1,3-butadiene derivatives are generated.
18. 10. Conditions for performing cycloaddition reactions will vary depending on the substrates chosen. A general procedure used for preparing many of the compounds listed in Table 1 is as follows: Polymer-supported silyloxydienes were shaken under an inert atmosphere in a methylene chloride solution of N-phenylmaleimide (0.5 M, 10 equivalents, 25°C). After 14 h., the solution was drained, and the resin was washed with three 10-mL portions of methylene chloride to afford resin bound Diels-Alder adducts.
19. 11. Bednarski, M.; Danishefsky, S. J. Am. Chem. Soc. 1983, 105, 3716.
20. 12. Hu, Y.; Porco, J. A. Tetrahedron Lett. 1999, 40, see following paper.