Catalytic addition of metallo-aldehyde enolates to ketones: A new C-C bond-forming hydrogenation

Organic Letters

Volumn 6, Issue 5, 2004, Pages 691-694

  Koech, Phillip K ^a   Krische, Michael J ^a  

^a UNIVERSITY OF TEXAS AT AUSTIN   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ALDEHYDE DERIVATIVE; ALKADIENE; ALKYNE DERIVATIVE; KETONE DERIVATIVE; RHODIUM;

ADDITION REACTION; ALDOL REACTION; ARTICLE; CATALYSIS; CHEMICAL ANALYSIS; CHEMICAL BOND; CHEMICAL MODIFICATION; HYDROGENATION; REACTION ANALYSIS;

ALCOHOLS; ALDEHYDES; CATALYSIS; HETEROCYCLIC COMPOUNDS; HYDROGENATION; KETONES; MOLECULAR STRUCTURE; OXIDATION-REDUCTION; RHODIUM; STEREOISOMERISM;

EID: 1642365601     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol030136c     Document Type: Article

References (18)

1. (a) Jang, H.-Y.; Huddleston, R. R.; Krische, M. J. J. Am. Chem. Soc. 2002, 124, 15156.
2. (b) Huddleston, R. R.; Krische, M. J. Org. Lett. 2003, 5, 1143.
3. Jang, H.-Y.; Huddleston, R. R.; Krische, M. J. Angew. Chem., Int. Ed. 2003, 42, 4074.
4. Huddleston, R. R.; Jang, H.-Y.; Krische, M. J. J. Am. Chem. Soc. 2003, 125, 11488.
5. (a) Heathcock, C. H. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Heathcock, C. H., Eds.; Pergamon Press: New York, 1991; Vol. 2, p 133.
6. (b) Alcaide, B.; Almendros, P. Angew. Chem., Int. Ed. 2003, 42, 858.
7. (a) Northrup, A. B.; MacMillan, D. W. C. J. Am. Chem. Soc. 2002, 124, 6798.
8. (b) Pidathala, C.; Hoang, L.; Vignola, N.; List, B. Angew. Chem., Int. Ed. 2003, 42, 2785.
9. Denmark, S.; Ghosh, S. K. Angew. Chem., Int. Ed. 2001, 40, 4759.
10. Yachi, K.; Shinokubo, H.; Oshima, K. J. Am. Chem. Soc. 1999, 121, 9465.
11. 3 also derived from acetaldehyde and acetone is -10.455 kcal/mol.
12. The failure of tris(dialkylamino)sulfonium enolates to react with aldehydes is attributed to unfavorable enolate-aldolate equilibria: Noyori, R.; Nishida, I.; Sakata, J.; Nishizawa, M. J. Am. Chem. Soc. 1980, 102, 1223.
13. Heathcock et al. reveal that the kinetic stereoselectivity in the addition of both Z-and E-lithium enolates of propanal to benzaldehyde gives 1:1 mixtures of syn-and anti-aldol products. Given that Z-lithium ketone enolates generally exhibit good levels of syn-diastereoselectivity in aldol additions, this result underscores the lack of stereoselectivity inherent to aldol additions employing aldehyde enolates: Heathcock, C. H.; Buse, C. T.; Kleschick, W. A.; Pirrung, M. C.; Sohn, J. E.; Lampe, J. J. Org. Chem. 1980, 45, 1066.
14. For a review on the heterolytic activation of elemental hydrogen, see: Brothers, P. J. Prog. Inorg. Chem. 1981, 28, 1.
15. Initiation of monohydride-based hydrogenation cycles via deprotonation of cationic Rh(III)-dihydrides is known: (a) Schrock, R. R.; Osborn, J. A. J. Am. Chem. Soc. 1976, 98, 2134. (b) Schrock, R. R.; Osborn, J. A. J. Am. Chem. Soc. 1976, 98, 2143. (c) Schrock, R. R.; Osborn, J. A. J. Am. Chem. Soc. 1976, 98, 4450.
16. Initiation of monohydride-based hydrogenation cycles via deprotonation of cationic Rh(III)-dihydrides is known: (a) Schrock, R. R.; Osborn, J. A. J. Am. Chem. Soc. 1976, 98, 2134. (b) Schrock, R. R.; Osborn, J. A. J. Am. Chem. Soc. 1976, 98, 2143. (c) Schrock, R. R.; Osborn, J. A. J. Am. Chem. Soc. 1976, 98, 4450.
17. Initiation of monohydride-based hydrogenation cycles via deprotonation of cationic Rh(III)-dihydrides is known: (a) Schrock, R. R.; Osborn, J. A. J. Am. Chem. Soc. 1976, 98, 2134. (b) Schrock, R. R.; Osborn, J. A. J. Am. Chem. Soc. 1976, 98, 2143. (c) Schrock, R. R.; Osborn, J. A. J. Am. Chem. Soc. 1976, 98, 4450.
18. For a review on the acidity of metal hydrides, see: Norton, J. R. In Transition Metal Hydrides; Dedieu, A., Ed.: VCH Publishers: New York, 1992; Chapter 9.