Catalytic enantioselective synthesis of β-lactams: Intramolecular Kinugasa reactions and interception of an intermediate in the reaction cascade

Angewandte Chemie - International Edition

Volumn 42, Issue 34, 2003, Pages 4082-4085

  Shintani, Ryo ^a   Fu, Gregory C ^a  

^a MASSACHUSETTS INSTITUTE OF TECHNOLOGY   (United States)

Author keywords

Asymmetric catalysis; Copper; Cyclizations; Domino reactions; Nitrogen heterocycles

Indexed keywords

CATALYST SELECTIVITY; CHEMICAL BONDS; SYNTHESIS (CHEMICAL);

ENANTIOSELECTIVITY;

CATALYSIS;

BETA LACTAM ANTIBIOTIC; COPPER DERIVATIVE; OXAZOLINE DERIVATIVE; TRIBACTAM;

ARTICLE; CATALYSIS; CATALYST; CHEMICAL BOND; CHIRALITY; DRUG STRUCTURE; DRUG SYNTHESIS; ENANTIOSELECTIVITY; MOLECULAR INTERACTION; REACTION ANALYSIS; STEREOCHEMISTRY; STRUCTURE ANALYSIS;

BETA-LACTAMS; CATALYSIS; COPPER; MOLECULAR STRUCTURE; STEREOISOMERISM;

EID: 0141788715     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200352103     Document Type: Article

References (46)

1. For discussions of the biological activity of β-lactams, see: a) Comprehensive Heterocyclic Chemistry II (Eds.: A. R. Katritzky, C. W. Rees, E. F. V. Scriven), Pergamon, New York, 1996, chap. 1.18-1.20; b) The Chemistry of β-Lactams (Ed.: M. I. Page), Blackie Academic & Professional, New York, 1992; c) Chemistry and Biology of β-Lactam Antibiotics, Vol. 1-3 (Eds.: R. B. Morin, M. Gorman), Academic Press, New York, 1982.
2. For discussions of the biological activity of β-lactams, see: a) Comprehensive Heterocyclic Chemistry II (Eds.: A. R. Katritzky, C. W. Rees, E. F. V. Scriven), Pergamon, New York, 1996, chap. 1.18-1.20; b) The Chemistry of β-Lactams (Ed.: M. I. Page), Blackie Academic & Professional, New York, 1992; c) Chemistry and Biology of β-Lactam Antibiotics, Vol. 1-3 (Eds.: R. B. Morin, M. Gorman), Academic Press, New York, 1982.
3. For discussions of the biological activity of β-lactams, see: a) Comprehensive Heterocyclic Chemistry II (Eds.: A. R. Katritzky, C. W. Rees, E. F. V. Scriven), Pergamon, New York, 1996, chap. 1.18-1.20; b) The Chemistry of β-Lactams (Ed.: M. I. Page), Blackie Academic & Professional, New York, 1992; c) Chemistry and Biology of β-Lactam Antibiotics, Vol. 1-3 (Eds.: R. B. Morin, M. Gorman), Academic Press, New York, 1982.
4. For reviews on the synthetic organic chemistry of β-lactams, see: a) Synthesis of β-Lactam Antibiotics: Chemistry, Biocatalysis and Process Integration (Ed.: A. Bruggink), Kluwer, Dordrecht, Netherlands, 2001; b) Enantioselective Synthesis of β-Amino Acids (Ed.: E. Juaristi), VCH, New York, 1997; c) I. Ojima, F. Delaloge, Chem. Soc. Rev. 1997, 26, 377-386; d) The Organic Chemistry of β-Lactams (Ed.: G. I. Georg), VCH, New York, 1993.
5. For reviews on the synthetic organic chemistry of β-lactams, see: a) Synthesis of β-Lactam Antibiotics: Chemistry, Biocatalysis and Process Integration (Ed.: A. Bruggink), Kluwer, Dordrecht, Netherlands, 2001; b) Enantioselective Synthesis of β-Amino Acids (Ed.: E. Juaristi), VCH, New York, 1997; c) I. Ojima, F. Delaloge, Chem. Soc. Rev. 1997, 26, 377-386; d) The Organic Chemistry of β-Lactams (Ed.: G. I. Georg), VCH, New York, 1993.
6. For reviews on the synthetic organic chemistry of β-lactams, see: a) Synthesis of β-Lactam Antibiotics: Chemistry, Biocatalysis and Process Integration (Ed.: A. Bruggink), Kluwer, Dordrecht, Netherlands, 2001; b) Enantioselective Synthesis of β-Amino Acids (Ed.: E. Juaristi), VCH, New York, 1997; c) I. Ojima, F. Delaloge, Chem. Soc. Rev. 1997, 26, 377-386; d) The Organic Chemistry of β-Lactams (Ed.: G. I. Georg), VCH, New York, 1993.
7. For reviews on the synthetic organic chemistry of β-lactams, see: a) Synthesis of β-Lactam Antibiotics: Chemistry, Biocatalysis and Process Integration (Ed.: A. Bruggink), Kluwer, Dordrecht, Netherlands, 2001; b) Enantioselective Synthesis of β-Amino Acids (Ed.: E. Juaristi), VCH, New York, 1997; c) I. Ojima, F. Delaloge, Chem. Soc. Rev. 1997, 26, 377-386; d) The Organic Chemistry of β-Lactams (Ed.: G. I. Georg), VCH, New York, 1993.
8. a) S. B. Rosenblum, T. Huynh, A. Afonso, H. R. Davis, Jr., N. Yumibe, J. W. Clader, D. A. Burnett, J. Med. Chem. 1998, 41, 973-980;
9. b) M. J. M. Darkes, R. M. Poole, K. L. Goa, Am. J. Cardiovasc. Drugs 2003, 3, 67-76;
10. http://custom.marketwatch.com/custom/excite-com/news-story.asp?guid= {4EB90E73-AC13-43B8-841D-E907016B2F85}.
11. For leading references, see: a) D. G. I. Kingston, Chem. Commun. 2001, 867-880;
12. b) D. G. I. Kingston, P. G. Jagtap, H. Yuan, L. Samala, Prog. Chem. Org. Nat. Prod. 2002, 84, 53-225.
13. For leading references, see: a) P. A. Magriotis, Angew. Chem. 2001, 113, 4507-4509; Angew. Chem. Int. Ed. 2001, 40, 4377-4379;
14. For leading references, see: a) P. A. Magriotis, Angew. Chem. 2001, 113, 4507-4509; Angew. Chem. Int. Ed. 2001, 40, 4377-4379;
15. b) B. L. Hodous, G. C. Fu, J. Am. Chem. Soc. 2002, 124, 1578-1579.
16. Their original report describes the stoichiometric reaction of a copper acetylide with a nitrone: M. Kinugasa, S. Hashimoto, J. Chem. Soc. Chem. Commun. 1972, 466-467.
17. M. Miura, M. Enna, K. Okuro, M. Nomura, J. Org. Chem. 1995, 60, 4999-5004.
18. For examples of applications of the Kinugasa reaction by others, see: a) L. K. Ding, W. J. Irwin, J. Chem. Soc. Perkin Trans. 1 1976, 2382-2386;
19. b) D. K. Dutta, R. C. Boruah, J. S. Sandhu, Indian J. Chem. Sect. B 1986, 25, 350-353; D. K. Dutta, R. C. Boruah, J. S. Sandhu, Heterocycles 1986, 24, 655-658;
20. b) D. K. Dutta, R. C. Boruah, J. S. Sandhu, Indian J. Chem. Sect. B 1986, 25, 350-353; D. K. Dutta, R. C. Boruah, J. S. Sandhu, Heterocycles 1986, 24, 655-658;
21. c) A. Basak, G. Bhattacharya, H. M. M. Bdour, Tetrahedron 1998, 54, 6529-6538;
22. d) A. Basak, S. C. Ghosh, T. Bhowmich, A. K. Das, V. Bertolasi, Tetrahedron Lett. 2002, 43, 5499-5501.
23. M. M.-C. Lo, G. C. Fu, J. Am. Chem. Soc. 2002, 124, 4572-4573.
24. For reviews of the chemistry and the biology of trinems/ tribactams, see: a) M. Gomez-Gallego, M. J. Mancheno, M. A. Sierra, Tetrahedron 2000, 56, 5743-5774;
25. b) C. Ghiron, T. Rossi, Targets Heterocycl. Syst. 1997, 1, 161-186;
26. c) S. Biondi, Spec. Publ. R. Soc. Chem. 1997, 198, 86-100;
27. d) A. Perboni, B. Tamburini, T. Rossi, D. Donati, G. Tarzia, G. Gaviraghi, Spec. Publ. R. Soc. Chem. 1993, 119, 21-35.
28. For an overview of the biological activity and the synthesis of 2-aminocycloalkyl carboxylic acid derivatives, see: F. Fülöp, Chem. Rev. 2001, 101, 2181-2204.
29. a) R. K. Bakshi, K. J. Barakat, Y. Lai, R. P. Nargund, B. L. Palucki, M. K. Park, A. A. Patchet, I. Sebhat, Z. Ye, WO US 25757 20010817, 2001;
30. b) R. K. Bakshi, R. P. Nargund, Z. Ye, WO US 17014 20010525, 2001.
31. 2-symmetric bisoxazolines in asymmetric catalysis, see: A. K. Ghosh, P. Mathivanan, J. Cappiello, Tetrahedron: Asymmetry 1998, 9, 1-45;
32. b) for some leading references to copper-catalyzed reactions, see: T. Rovis, D. A. Evans, Prog. Inorg. Chem. 2001, 50, 1-150.
33. Similarly, in the only study by others of a catalytic asymmetric Kinugasa reaction, Miura et al. found bisoxazoline 4 to be only modestly effective as a chiral ligand for copper-catalyzed intermolecular couplings of alkynes with nitrones (maximum ee value: 57%).[7]
34. a) R. Shintani, M. M.-C. Lo, G. C. Fu, Org. Lett. 2000, 2, 3695-3697;
35. b) R. Shintani, G. C. Fu, Org. Lett. 2002, 4, 3699-3702.
36. The data for ligands 5a and 6 in Table 1 (entries 3 and 5) indicate that the central chirality of the oxazoline subunit is the dominant stereocontrol element and that the planar chirality of the phosphaferrocene subunit plays a subordinate, although significant, role.
37. The absolute configuration of the product was determined through X-ray crystallographic analysis of the bis(amide) that is produced upon the reaction of β-lactam 3 with excess 2-bromobenzylamine (see Supporting Information).
38. 2O enhances the ee value (> 99 % ee; 53% recovery).
39. Ligands 5a and 5b promote similar enantioselectivity in the synthesis of 6,4 bicyclic systems (Table 2, entries 1-4). However, the yields are generally higher when 5a is employed. For the synthesis of 7,4 bicyclic systems (Table 2, entries 5 and 6), comparable yields were observed when ligands 5a or 5b were used, but somewhat better ee values (up to 15% higher) were observed in the presence of ligand 5b.
40. We believe that this proceeds through ring-opening fragmentation to a ketene, followed by recyclization; see: C. Ahn, J. W. Kennington, Jr., P. DeShong, J. Org. Chem. 1994, 59, 6282-6286.
41. For a recent review of catalytic asymmetric methods for the generation of quaternary stereocenters, see: E. J. Corey, A. Guzman-Perez, Angew. Chem. 1998, 110, 402-415; Angew. Chem. Int. Ed. 1998, 37, 388-401; see also: J. Christoffers, A. Mann, Angew. Chem. 2001, 113, 4725-4732; Angew. Chem. Int. Ed. 2001, 40, 4591-4597.
42. For a recent review of catalytic asymmetric methods for the generation of quaternary stereocenters, see: E. J. Corey, A. Guzman-Perez, Angew. Chem. 1998, 110, 402-415; Angew. Chem. Int. Ed. 1998, 37, 388-401; see also: J. Christoffers, A. Mann, Angew. Chem. 2001, 113, 4725-4732; Angew. Chem. Int. Ed. 2001, 40, 4591-4597.
43. For a recent review of catalytic asymmetric methods for the generation of quaternary stereocenters, see: E. J. Corey, A. Guzman-Perez, Angew. Chem. 1998, 110, 402-415; Angew. Chem. Int. Ed. 1998, 37, 388-401; see also: J. Christoffers, A. Mann, Angew. Chem. 2001, 113, 4725-4732; Angew. Chem. Int. Ed. 2001, 40, 4591-4597.
44. For a recent review of catalytic asymmetric methods for the generation of quaternary stereocenters, see: E. J. Corey, A. Guzman-Perez, Angew. Chem. 1998, 110, 402-415; Angew. Chem. Int. Ed. 1998, 37, 388-401; see also: J. Christoffers, A. Mann, Angew. Chem. 2001, 113, 4725-4732; Angew. Chem. Int. Ed. 2001, 40, 4591-4597.
45. +).
46. 2NMe, acetophenone is presumably generated, rather than a trialkylammonium salt. Acetophenone is a poor proton donor compared to a trialkylammonium salt.