Synthesis of Symmetrical Trisubstituted Olefins by Cross Metathesis

Organic Letters

Volumn 4, Issue 11, 2002, Pages 1939-1942

  Chatterjee, Arnab K ^a   Sanders, Daniel P ^a   Grubbs, Robert H ^a  

^a California Institute of Technology   (United States)

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ARTICLE;

EID: 0001754263     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol0259793     Document Type: Article

References (32)

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3. (c) Wang, Q.; Wei, H.; Schlosser, M. Eur. J. Org. Chem. 1999, 3263.
4. (a) Furstner, A. Angew. Chem., Int. Ed. 2000, 39, 3013.
5. (b) Trnka, T. M.; Grubbs, R. H. Acc. Chem. Res. 2001, 34, 18.
6. (c) Kotha, S.; Sreenivasachary, N. Ind. J. Chem. B 2001, 40, 763.
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8. (b) Bazan, G. C.; Khosravi, E.; Schrock, R. R.; Feast, W. J.; Gibson, V. C.; O'Regan, M. B.; Thomas, J. K.; Davis, W. M. J. Am. Chem. Soc. 1990, 112, 8378.
9. (c) Bazan, G. C.; Oskam, J. H.; Cho. H. N.; Park, L. Y.; Schrock, R. R. J. Am. Chem. Soc. 1991, 113, 6899.
10. (a) Schwab, P.; France, M. B.; Ziller, J. W.; Grubbs, R. H. Angew. Chem., Int. Ed. Engl. 1995, 34, 2039.
11. (b) Schwab, P.; Grubbs, R. H.; Ziller, J. W. J. Am. Chem. Soc. 1996, 118, 100.
12. (c) Belderrain, T. R.; Grubbs, R. H. Organometallics 1997, 16, 4001.
13. Leading references using 1 and 2 in CM: (a) Crowe, W. E.; Goldberg, D. R. J. Am. Chem. Soc. 1995, 117, 5162. (b) Brummer, O.; Ruckert, A.; Blechert, S. Chem. Eur. J. 1997, 3, 441. (c) Blackwell, H. E.; O'Leary, D. J.; Chatterjee, A. K.; Washenfelder, R. A.; Bussmann, D. A.; Grubbs, R. H. J. Am. Chem. Soc. 2000, 122, 58.
14. Leading references using 1 and 2 in CM: (a) Crowe, W. E.; Goldberg, D. R. J. Am. Chem. Soc. 1995, 117, 5162. (b) Brummer, O.; Ruckert, A.; Blechert, S. Chem. Eur. J. 1997, 3, 441. (c) Blackwell, H. E.; O'Leary, D. J.; Chatterjee, A. K.; Washenfelder, R. A.; Bussmann, D. A.; Grubbs, R. H. J. Am. Chem. Soc. 2000, 122, 58.
15. Leading references using 1 and 2 in CM: (a) Crowe, W. E.; Goldberg, D. R. J. Am. Chem. Soc. 1995, 117, 5162. (b) Brummer, O.; Ruckert, A.; Blechert, S. Chem. Eur. J. 1997, 3, 441. (c) Blackwell, H. E.; O'Leary, D. J.; Chatterjee, A. K.; Washenfelder, R. A.; Bussmann, D. A.; Grubbs, R. H. J. Am. Chem. Soc. 2000, 122, 58.
16. (a) Scholl, M.; Ding, S.; Lee, C. W.; Grubbs, R. H. Org. Lett. 1999, 1, 953.
17. (b) Sanford, M. S.; Love, J. A.; Grubbs, R. H. J. Am. Chem. Soc. 2001, 123, 6543.
18. (a) Chatterjee, A. K.; Morgan, J. P.; Scholl, M.; Grubbs, R. H. J. Am. Chem. Soc. 2000, 122, 3783.
19. (b) Choi, T.-L.; Chatterjee, A. K.; Grubbs, R. H. Angew. Chem., Int. Ed. 2000, 39, 1277.
20. (c) Choi, T.-L.; Lee, C. W.; Chatterjee, A. K.; Grubbs, R. H. J. Am. Chem. Soc. 2001, 123, 10417.
21. Chatterjee, A. K.; Choi, T.-L.; Grubbs, R. H. Synlett 2001, 1034.
22. Grela, K.; Bieniek, M. Tetrahedron Lett. 2001, 42, 6425.
23. Chatterjee, A. K.; Grubbs, R. H. Org. Lett. 1999, 1, 1751.
24. Some of these olefins have been demonstrated in other CM systems from this group, see: ref 7c and Goldberg, S. D.; Grubbs, R. H. Angew. Chem., Int. Ed. 2002, 41, 807.
25. Typical isobutylene CM procedure: To an oven dried, 100 mL Fischer-Porter bottle with Teflon stir bar, ruthenium metathesis catalyst (15.0 mg, 0.018 mmol, 1.0 mol %) was added. The bottle was capped with a rubber septum and flushed with dry nitrogen and cooled to -78°C or temperature sufficient to freeze substrate). Substrate (1.0 mmol) was injected into the bottle. Once the substrate was frozen, a pressure regulator was attached to the bottle. The bottle was evacuated and backfilled with dry nitrogen 3 times. Subsequently, isobutylene (5-10 mL, 50-100 equiv) was condensed into the bottle. The bottle was backfilled to ∼2 psi with nitrogen, sealed, and allowed to slowly warm to room temperature, at which time it was transferred to an oil bath at 40°C. After stirring for 12-18 h, the bottle was removed from the oil bath and allowed to cool to room temperature. The isobutylene was slowly vented off at room temperature until the pressure apparatus could be safely disassembled. The remaining mixture was taken up in organic solvent for subsequent silica gel chromatography and/or spectrographic characterization.
26. The following paper provides an excellent application ot the methods described in this Letter in an allyl to prenyl conversion, see: Spessard, S. J.; Stoltz, B. M. Org. Lett. 2002, 4, 1943.
27. Typical 2-methyl-2-butene procedure (Table 2, entry 4): Pentafluoroallylbenzene (225 μL, 1.468 mmol) from Aldrich Chem. Co. and 2-methyl-2-butene (3.2 mL) from Aldrich Chem. Co. were added simultaneously via syringe to a stirring solution of catalyst 3 (1.25 mg, 0.015 mmol, 1.0 mol %) under a nitrogen atmosphere. The flask was allowed to stir at room temperature for 12 h. The reaction mixture was then reduced in volume to 0.5 mL and purified directly on a silica gel column (2 × 10 cm), eluting with 20:1 hexane:ethyl acetate to provide the cross-metathesis product (316 mg, 1.337 mmol, 91% yield) as a viscous oil.
28. Thermodynamically controlled disproportionation of 2-methyl-2-butene and the step-growth ADMET polymerization of 2-methyl-1,5-hexadiene have been reported with 1: Konzelman, J.; Wagener, K. B. Macromolecules 1995, 28, 4686.
29. 2-Cy) undergoes one turnover with 2-methyl-2-pentene to generate the ruthenium propylidene and dimethyl-substituted cyclohexyl acrylate. Ulman, M.; Belderrain, T. R.; Grubbs, R. H. Tetrahedron Lett. 2000, 41, 4689.
30. Metathesis depolymerization of polyisoprene has been previously reported with 3: Craig, S. W.; Manzer, J. A.; Coughlin, E. B. Macromolecules 2001, 34, 7929.
31. 1H NMR in the reactions with 2-methyl-2-butene.
32. Column chromatography yielded a 6:1 ratio of dimethyl-substituted to methyl-substituted cross-products. Resubjection of the product mixture to CM conditions with 2-methyl-2-butene failed to improve the conversion of the dimethyl-substituted product.