Thioamides via thiatriazolines

Tetrahedron Letters

Volumn 47, Issue 7, 2006, Pages 1163-1166

  Kolakowski, Robert V ^a   Shangguan, Ning ^a   Williams, Lawrence J ^a  

^a RUTGERS UNIVERSITY   (United States)

Author keywords

Amidation; Azides; Thiatriazolines; Thioacids; Thioamides

Indexed keywords

AZIDE; THIOAMIDE;

ARTICLE; CHEMICAL REACTION; CHEMICAL STRUCTURE; FRAGMENTATION REACTION; SYNTHESIS;

EID: 30644469662     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/j.tetlet.2005.12.020     Document Type: Article

References (45)

1. T.S. Jagodzinski Chem. Rev. 103 2003 197 227
2. For recent amide thionations see: A.B. Charette, and M. Grenon J. Org. Chem. 68 2003 5792 5794
3. S.J. Coats, J.S. Link, and D.J. Hlasta Org. Lett. 5 2003 721 724
4. O.I. Zbruyev, N. Stiasni, and C.O. Kappe J. Comb. Chem. 5 2003 145 148
5. T.J. Curphey J. Org. Chem. 67 2002 6461 6473
6. P. Ilankumaran, A.R. Ramesha, and S. Chandrasekaran Tetrahedron Lett. 36 1995 8311 8314
7. For an important report, see: G. Lajoie, F. Lepine, L. Mazaik, and B. Belleau Tetrahedron Lett. 24 1983 3815 3818
8. For other approaches using dithiocarboxylates or isothiacyanates see: E. Schaumann B.M. Trost I. Fleming Comprehensive Organic Synthesis Vol. 6 1991 Pergamon Press Oxford 419 432
9. E. Schaumann, M. Moeller, and G. Adiwidjaja Chem. Ber. 121 1988 689 699
10. E.P. Papadopoulos J. Org. Chem. 41 1975 962 965
11. For an interesting side reaction that was noted to produce a thioamide see: H. Paulsen, T. Bielfeldt, S. Peters, and K. Bock Liebigs Ann. Chem. 1994 369
12. N. Shangguan, S. Katukojvala, R. Greenberg, and L.J. Williams J. Am. Chem. Soc. 125 2003 7754 7755
13. The thio acid/azide amidation does not involve in situ reduction of azide to amine; see Ref. 3.
14. For a combined experimental and computational mechanistic study of the thioacid/azide amidation, see: Kokakowski, R. V.; Shangguan, N.; Wang, Z.; Sauers, R. R.; Williams, L. J., submitted for publication.
15. This amidation approaches the ideal 'click' reaction for electron deficient azides, see: H.C. Kolb, M.G. Finn, and K.B. Sharpless Angew. Chem., Int. Ed. 40 2001 2004 2021
16. G. Lewis Warren, G. Green Luke, F. Grynszpan, Z. Radic, R. Carlier Paul, P. Taylor, M.G. Finn, and K.B. Sharpless Angew. Chem., Int. Ed. 41 2002 1053 1057
17. Z.P. Demko, and K.B. Sharpless Angew. Chem., Int. Ed. 41 2002 2110 2113
18. B.-C. Suh, H. Jeon, G.H. Posner, and S.M. Silverman Tetrahedron Lett. 45 2004 4623 4625
19. See also: K. Tani, S.-i. Hanabusa, S. Kato, S.-y. Mutoh, S.-i. Suzuki, and M. Ishida J. Chem. Soc., Dalton Trans. 2001 518 527
20. S. Kato, Y. Ono, K. Miyagawa, T. Murai, and M. Ishida Tetrahedron Lett. 27 1986 4595 4598
21. S. Kato, H. Shibahashi, T. Katada, T. Takagi, I. Noda, M. Mizuta, and M. Goto Liebigs Ann. Chem. 7 1982 1229 1408
22. J. Houben Ber 39 1906 3219
23. For general procedures, see: D.F. Aycock, and G.R. Jurch Jr. J. Org. Chem. 44 1979 569 572 The dithioacids were prepared according to Aycock et al., and used without further purification. CAUTION: Carbon disulfide vapors are malodorous and cause liver and kidney damage upon inhalation. This reagent is flammable, low boiling, and should be handled in a well-ventilated hood. STENCH: Dithioacids should be handled in a well-ventilated hood
24. + 242.0, found: 242.1.
25. W. Walter, and A. Roehr Liebigs Ann. Chem. 1975 41 53
26. M.P. Cava, and M.I. Levinson Tetrahedron 41 1985 5061 5087
27. A.A. Santilli, A.C. Scotese, R.L. Morris, G.A. Schiehser, D.M. Teller, S.T. Nielsen, and D.P. Strike J. Med. Chem. 31 1988 1480 1486
28. D. Brillon Synth. Commun. 20 1990 3085 3095
29. M. Jesberger, T.P. Davis, and L. Barner Synthesis 2003 1929 1958
30. F.R. Meadow, and J.C. Cavagnol J. Org. Chem. 16 1951 1582 1585
31. Dithiobenzoic anhydride (4 ), which forms upon exposure of dithiobenzoic acid to air and light, is observed as an impurity in the reagent. The levels of 4, as monitored by GCMS, rapidly increased significantly above background levels during the reaction. In principle, it would be possible for lutidine to add to I. Fragmentation of the tetrahedral intermediate could give the N-acyllutidinium ion, nitrogen, sulfur, and 3. Attack on the N-acyllutidinium intermediate by 1 would lead to the observed products. However, this type of side reaction is not observed in the parent thioacid/azide amidation where, given the higher reactivity of a carbonyl over a thiocarbonyl, such a pathway would be more facile than in the present context. Moreover, the intermediacy of an N-acyllutidinium species is unlikely: addition of lutidine to the thiocarbonyl of I would be slow, yet the velocity of the reaction presented here is high.
32. The alternative mechanism, wherein dithiobenzoic anhydride is formed as in path A and then reacts with piperidine to give the observed acylation product (5 ) and benzenesulfonamide (3 ), can be ruled out, as 3 is not generated in significant quantities in the presence of triethylamine (see path C), and 3 is not acylated by dithiobenzoic anhydride.
33. E. Lieber, E. Oftedahl, and C.N.R. Rao J. Am. Chem. Soc. 28 1963 194 198
34. E.V. Loock, J.-M. Vandensavel, G. L'abbe, and G. Smets J. Org. Chem. 38 1973 2916
35. G. L'abbe, G. Verhelst, C.-C. Yu, and S. Toppet J. Org. Chem. 40 1975 1728
36. G. L'abbe Angew. Chem., Int. Ed. Engl. 19 1980 276
37. G. L'Abbe, J.P. Dekerk, C. Martens, and S. Toppet J. Org. Chem. 45 1980 4366 4371
38. G. L'abbe, P. Brems, and E. Albrecht J. Heterocycl. Chem. 27 1990 1059
39. C. Wentrup, and P. Kambouris Chem. Rev. 91 1991 363
40. W. Adam, and R.M. Bargon Eur. J. Org. Chem. 2001 1959
41. S. Punna, and M.G. Finn Synlett 2004 99 100
42. S. Knapp, and E. Darout Org. Lett. 7 2005 203 206
43. F. Fazio, and C.-H. Wong Tetrahedron Lett. 44 2003 9083 9085
44. X. Zhu, K. Pachamuthu, and R.R. Schmidt Org. Lett. 6 2004 1083 1085
45. R. Merkx, A.J. Brouwer, D.T.S. Rijkers, and R.M.J. Liskamp Org. Lett. 7 2005 1125 1128