Direct catalytic aldol-type reactions using RCH2CN

Organic Letters

Volumn 5, Issue 17, 2003, Pages 3147-3150

  Suto, Yutaka ^a   Kumagai, Naoya ^a   Matsunaga, Shigeki ^a   Kanai, Motomu ^a,b   Shibasaki, Masakatsu ^a  

^a UNIVERSITY OF TOKYO   (Japan)

^b JAPAN SCIENCE AND TECHNOLOGY AGENCY   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

ALDEHYDE DERIVATIVE; COPPER DERIVATIVE; COPPER FLUORIDE; ESTER DERIVATIVE; KETONE DERIVATIVE; NITRILE; UNCLASSIFIED DRUG;

ALDOL REACTION; ARTICLE; CATALYSIS; ENANTIOSELECTIVITY; METHYLATION;

EID: 0141631816     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol035206u     Document Type: Article

References (28)

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2. For examples of cyanomethylation in natural product synthesis, see: (a) Corey, E. J.; Wu, Y.-J. J. Am. Chem. Soc. 1993, 115, 8871. (b) Fukuda, Y.; Okamoto, Y. Tetrahedron 2002, 58, 2513.
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5. For a review on direct catalytic enantioselective aldol reactions, see: List, B. Tetrahedron 2002, 58, 5573.
6. For a direct catalytic enantioselective alkynylation, see: Anand, N. K.; Carreira, E. M. J. Am. Chem. Soc. 2001, 123, 9687.
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9. Soai, K.; Hirose, Y.; Sakata, S. Tetrahedron: Asymmetry 1992, 3, 677. The product with 78% ee was obtained in 45% yield, using 30 mol % catalyst (only one example from benzaldehyde).
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11. 2CN than in allyltrimethylsilane.
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13. Initial product was the corresponding triethoxysilyl ether.
14. Slow addition time is important for high chemical yield. See Supporting Information (SI) for details.
15. 3 (0.3 mL) was added for desilylation (ca. 1 h).
16. There are no previous examples of catalytic cyanomethylation of linear aldehydes, propiophenone, or enones.
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18. 19F NMR.
19. Alkaline metal free CuO′Bu was prepared by adding 1 equiv of ′BuOH to mesitylcopper generated by Saegusa's method: Tsuda, T.; Watanabe, K.; Miyata, K.; Yamamoto, H.; Saegusa, T. Inorg. Chem. 1981, 20, 2728. CuO′Bu can be stored as a THF solution (0.5 M) at -30°C in a freezer under an argon atmosphere for at least two months without any activity loss.
20. In the previous study of ketone aldol reaction (ref 8), we noticed the importance of the phosphine ligand in the catalyst turnover step, in which a copper aldolate traps the silicon to form the silyl aldolate. This step might mimic the alkylnitrile deprotonation by the copper aldolate in the direct catalytic addition.
21. General Procedure for CuO′Bu-Catalyzed Direct Cyanomethylation of Aldehyde (Table 3, Entry 6). CuO′Bu (0.03 mmol, 60μL in THF) and dppe (18 mg, 0.045 mmol) were mixed and dried under vacuum for 1 h. To the residue were added DMSO (0.3 mL), propionitrile (0.3 mL), and 2h (30 μL, 0.3 mmol) to start the reaction.
22. Catalytic addition of alkylnitriles other than acetonitrile is novel. The reaction with ketones has not yet been achieved.
23. Canceill, J.; Jacques, J. Bull. Soc. Chim. Fr. 1970, 2180.
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27. For recent advances, see: (a) Evans, D. A.; Tedrow, J. S.; Shaw, J. T.; Downey, C. W. J. Am. Chem. Soc. 2001, 124, 392. (b) Evans, D. A.; Downey, C. W. ; Shaw, J. T.; Tedrow, J. S. Org. Lett. 2002, 4, 1127. (c) Evans, D. A.; Downey, C. W.; Hubbs, J. L. J. Am. Chem. Soc. 2003, 125, 8706.
28. For recent advances, see: (a) Evans, D. A.; Tedrow, J. S.; Shaw, J. T.; Downey, C. W. J. Am. Chem. Soc. 2001, 124, 392. (b) Evans, D. A.; Downey, C. W. ; Shaw, J. T.; Tedrow, J. S. Org. Lett. 2002, 4, 1127. (c) Evans, D. A.; Downey, C. W.; Hubbs, J. L. J. Am. Chem. Soc. 2003, 125, 8706.