Stereodivergent synthesis of β-lactams using thermal rearrangement of aminocyclobutenones

Organic Letters

Volumn 11, Issue 15, 2009, Pages 3266-3268

  Hachiya, Iwao ^a   Yoshitomi, Takuya ^a   Yamaguchi, Yukari ^a   Shimizu, Makoto ^a  

^a MIE UNIVERSITY   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

ACETAL DERIVATIVE; BETA LACTAM; ETHYLENE DERIVATIVE; IMINE; KETENE; KETONE;

ARTICLE; CATALYSIS; CHEMISTRY; STEREOISOMERISM; SYNTHESIS;

ACETALS; BETA-LACTAMS; CATALYSIS; ETHYLENES; IMINES; KETONES; STEREOISOMERISM;

EID: 68149091446     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol901192y     Document Type: Article

References (15)

1. Chemistry and Biology of β-Lactam Antibiotics; Morin, R. B., Gorman, M., Eds.; Academic Press: New York, 1982; Vols. 1-3.
2. For a review on the synthesis of β-lactams, see: Brandi, A.; Cicchi, S.; Cordera, F. M. Chem. Rev. 2008, 108, 3988.
3. For a review on the alkynyl imines in organic synthesis, see: Stadnichuk, M. D.; Khramchikhin, A. V.; Piterskaya, Yu. L.; Suvorova, I. V. Russ. J. Gen. Chem. 1999, 69, 593.
4. Shimizu, M.; Hachiya, I.; Mizota, I. Chem. Commun. 2009, 874.
5. For a recent example of thermal rearrangement of cyclobutenones, see: Harrowven, D. C.; Pascoe, D. D.; Guy, I. L. Angew. Chem., Int. Ed. 2007, 46, 425.
6. 2 gave the iminocyclobutenone in yields ranging from 8% to 25%.
7. 2 = Ph) gave the δ-lactam instead of the β-lactam.
8. 3,4; coupling constants for cis-β-lactams are larger than those for trans-isomers. See: Bouffard, F. A.; Johnston, D. B. R.; Christensen, B. G. J. Org. Chem. 1980, 45, 1130.
9. Among the solvents examined, such as toluene, xylene, octane, and chlorobenzene, octane was found to be the most effective.
10. Tang reported that an appropriate amine was essential in the Kinugasa reaction to control both diastereo- and enantioselectivities, in which the amine might coordinate to the copper and relay the chirality to the product; see: Ye, M.-C.; Zhou, J.; Tang, Y. J. Org. Chem. 2006, 71, 3576. For a similar aminoketene intermediate,
11. see: Ahn, C.; Kennington, J. W., Jr.; DeShong, P. J. Org. Chem. 1994, 59, 6282. Fu indicated that the Kinugasa reaction would proceed through ring-opening fragmentation to a ketene, followed by recyclization, where the role of the amine was thought to be both deprotonation of an acetylene with copper catalyst to generate the copper acetylide and protonation of the enolate;
12. see: Shintani, R.; Fu, G. C. Angew. Chem., Int. Ed. 2003, 42, 4082.
13. Regarding the role of 1,4-dimethylpiperazine (6), we presume the formation of a bulky proton source shown.
14. For a review on the biological activity of β-lactams, see: von Nussbaum, F.; Brands, M.; Hinzen, B.; Weigand, S.; Häbich, D. Angew. Chem., Int. Ed. 2006, 45, 5072.
15. For a review on the β-lactam synthon method, see: Alcaide, B.; Almendros, P.; Aragoncillo, C. Chem. Rev. 2007, 107, 4437.