Free-radical-based, specific desulfurization of cysteine: A powerful advance in the synthesis of polypeptides and glycopolypeptides

Angewandte Chemie - International Edition

Volumn 46, Issue 48, 2007, Pages 9248-9252

  Wan, Qian ^a   Danishefsky, Samuel J ^a,b  

^a MEMORIAL SLOAN KETTERING CANCER CENTER   (United States)

^b Columbia University ^*  (United States)

Author keywords

Glycopeptides; Native chemical ligation; Natural products; Peptides; Radical reactions

Indexed keywords

AMINO ACIDS; FUNCTIONAL GROUPS; POLYPEPTIDES; REACTION KINETICS; SYNTHESIS (CHEMICAL);

AQUEOUS MEDIUM; COMPLEX PEPTIDES; GLYCOPOLYPEPTIDES;

FREE RADICAL POLYMERIZATION;

CYSTEINE; FREE RADICAL; GLYCOPEPTIDE; PEPTIDE; SULFUR;

ARTICLE; CHEMISTRY; SYNTHESIS;

CYSTEINE; FREE RADICALS; GLYCOPEPTIDES; PEPTIDES; SULFUR;

EID: 37349094422     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200704195     Document Type: Article

References (44)

1. P. E. Dawson, T. W. Muir, I. Clark-Lewis, S. B. H. Kent, Science 1994, 266, 776-779.
2. a) D. S. Kemp, Biopolymers 1981, 20, 1793-1804;
3. b) R. I. Carey, D. S. Kemp, J. Org. Chem. 1993, 58, 2216-2222.
4. a) B. Wu, J. Chen, J. D. Warren, G. Chen, Z. Hua, S. J. Danishefsky, Angew. Chem. 2006, 118, 4222-4231;.
5. Chem. Int. Ed. 2006, 45, 4116-4125;
6. b) J. Chen, G. Chen, B. Wu, Q. Wan, Z. Tan, Z. Hua, S. J. Danishefsky, Tetrahedron Lett. 2006, 47, 8013-8016.
7. a) J. D. Warren, J. S. Miller, S. J. Keding, S. J. Danishefsky, J. Am. Chem. Soc. 2004, 126, 6576-6578;
8. b) G. Chen, J. D. Warren, J. Chen, B. Wu, Q. Wan, S. J. Danishefsky, J. Am. Chem. Soc. 2006, 128, 7460-7462.
9. G. Chen, Q. Wan, Z. Tan, C. Kan, Z. Hua, K. Ranganathan, S. J. Danishefsky, Angew. Chem. 2007, 119, 7527-7531;
10. Angew. Chem. Int. Ed. 2007, 46, 7383-7387.
11. L. Z. Yan, P. E. Dawson, J. Am. Chem. Soc. 2001, 123, 526-533, and references therein.
12. An extended NCL/phenylalanine desulfurization method was developed by two research groups recently: a) P. Botti, S. Tchertchian, WO 133962, 2006;
13. b) D. Crich, A. Banerjee, J. Am. Chem. Soc. 2007, 129, 10064-10065.
14. B. Pentelute, S. B. H. Kent, Org. Lett. 2007, 9, 687-690.
15. E. C. B. Johnson, E. Malito, Y. Shen, D. Rich, W. Tang, S. B. H. Kent, J. Am. Chem. Soc. 2007, 129, 11480-11490. All the methioline residues were mutated to prevent possible oxidation and desulfurization problems.
16. a) K. Nishide, Y. Shigeta, K. Obata, T. Inoue, M. Node, Tetrahedron Lett. 1996, 37, 2271-2274;
17. b) M. Node, K. Nishide, Y. Shigeta, K. Obata, H. Shiraki, H. Kunishige, Tetrahedron 1997, 53, 12883-12894, and references therein.
18. M. B. Smith, J. March, March's Advanced Organic Chemistry-Reactions, Mechanisms, and Structure, 6th ed., Wiley, Hoboken, 2007, pp. 1848-1850.
19. a) A. Brik, Y.-Y. Yang, S. Ficht, C.-H. Wong, J. Am. Chem. Soc. 2006, 128, 5626-5627;
20. b) A. Brik, S. Ficht, Y.-Y. Yang, C. S. Bennett, C.-H. Wong, J. Am. Chem. Soc. 2006, 128, 15026-15033;
21. 3 used.
22. J. Chen, unpublished results.
23. F. W. Hoffmann, R. J. Ess, T. C. Simmons, R. S. Hanzel, J. Am. Chem. Soc. 1956, 78, 6414.
24. a) C. Walling, R. Rabinowitz, J. Am. Chem. Soc. 1957, 79, 5326;
25. b) C. Walling, O. H. Basedow, E. S. Savas, J. Am. Chem. Soc. 1960, 82, 2181-2184.
26. a) A. González, G. Valencia, Tetrahedron: Asymmetry 1998, 9, 2761-2764;
27. b) J. Cuesta, G. Arsequell, G. Valencia, A. González, Tetrahedron: Asymmetry 1999, 10, 2643-2646;
28. c) G. Arsequell, A. González, G. Valencia, Tetrahedron Lett. 2001, 42, 2685-2687.
29. a) A. Schönberg, Ber. Dtsch. Chem. Ges. 1935, 68, 163-164;
30. b) J. A. Burns, J. C. Butler, J. Moran, G. M. Whitesides, J. Org. Chem. 1991, 56, 2648-2650.
31. I. S. Alferiev, J. M. Connolly, R. J. Levy, J. Organomet. Chem. 2005, 690, 2543-2547. Desulfurization was observed as an unexpected side reaction during the synthesis of mercaptobisphosphonate. We reason that there could also be a free-radical process occurring under basic conditions in the presence of air.
32. Other kinds of radical initiator, such as 2,2′-azobis(2- methylpropionamidine)dihydrochloride (V-50), have been investigated as well. V-50 can also initiate the radical desulfurization at RT.
33. a) D. Bang, B. L. Pentelute, S. B. H. Kent, Angew. Chem. 2006, 118, 4089-4092;
34. Angew. Chem. Int. Ed. 2006, 45, 3985-3988;
35. b) V. Y. Torbeev, S. B. H. Kent, Angew. Chem. 2007, 119, 1697-1700;
36. Angew. Chem. Int. Ed. 2007, 46, 1667-1670;
37. c) T. Durek, V. Y. Torbeev, S. B. H. Kent, Proc. Natl. Acad. Sci. USA 2007, 104, 4846-4851.
38. S. Quintyne-Walcott, A. R. Maxwell, W. Reynolds, J. Nat. Prod. 2007, 70, 1374-1376.
39. The details of the synthesis of crotogossamide are presented in the Supporting Information.
40. a) R. J. Hondal, B. L. Nilsson, R. T. Raines, J. Am. Chem. Soc. 2001, 123, 5140-5141;
41. b) R. Quaderer, D. Hilvert, Chem. Commun. 2002, 2620-2621.
42. Previous examples of radical-mediated reactions of cysteine-containing peptides have been described, but the desired alanyl peptide was produced and the undesired thioformimidate was generated at the same time: a) T. Saegusa, S. Kobayashi, Y. Ito, J. Org. Chem. 1970, 35, 2118-2121;
43. b) L. Benati, R. Leardini, M. Minozzi, D. Nanni, R. Scialpi, P. Spagnolo, S. Strazzari, G. Zanardi, Angew. Chem. 2004, 116, 3682-3685;
44. Angew. Chem. Int. Ed. 2004, 43, 3598-3601.