Direct Carbamoylation of Alkenyl Halides

Organic Letters

Volumn 5, Issue 26, 2003, Pages 4947-4949

  Cunico, Robert F ^a   Maity, Bikash C ^a  

^a NORTHERN ILLINOIS UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ALKENYL GROUP; BROMIDE; CHLORIDE; HALIDE; PALLADIUM COMPLEX; PHOSPHINE; SILANE DERIVATIVE; TOLUENE;

ARTICLE; CARBAMOYLATION; CATALYSIS; CATALYST; CHEMICAL REACTION; COMPLEX FORMATION; REACTION ANALYSIS; TEMPERATURE SENSITIVITY;

EID: 0347286694     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol030110l     Document Type: Article

References (35)

1. Schoenberg, A.; Heck, R. F. J. Org. Chem. 1974, 39, 3327-3331.
2. (a) Skoda-Földes, R.; Kollár, L. Curr. Org. Chem. 2002, 6, 1097-1119.
3. (b) Beller, M.; Indolese, A. F. Chimia 2001, 55, 684-687.
4. (c) Yamamoto, A.; Kayaki, Y.; Nagayama, K.; Shimizu, I. Synlett 2000, 925-937.
5. (d) Soderberg, B. C. In Comprehensive Organometallic Chemistry II; Hegedus, L. S., Abel, E. W., Stone, F. G. A., Wilkinson, G., Eds.; Pergamon: Oxford, 1995; Vol. 12, pp 249-251.
6. (e) Tsuji, J. Palladium Reagents and Catalysis; Wiley: Chichester, 1995; pp 196-198.
7. (f) Colquhoun, H. M.; Thompson, D. J.; Twigg, M. V. Carbonylation; Plenum: New York, 1991; pp 145-149.
8. Cunico, R. F.; Maity, B. C. Org. Lett. 2002, 4, 4357-4359.
9. 3).
10. 6-DBU).
11. 3).
12. (a) Wan, Y.; Alterman, M.; Larhed, M.; Hallberg, A. J. Comb. Chem. 2003, 5, 82-84 (employed formamide-KOtBu).
13. (b) Wan, Y.; Alterman, M.; Larhed, M.; Hallberg, A. J. Org. Chem. 2002, 67, 6232-6235 (employed DMF-KOtBu).
14. Morimoto, T.; Fujioka, M.; Fuji, K.; Tsutsumi, K.; Kakiuchi, K. Chem. Lett. 2003, 32, 154-155 (employed decarbonylatable aldehydes).
15. Cunico, R. F.; Chen, J. Synth. Commun. 2003, 33, 1963-1968.
16. 2Si: C, 64.11; H, 8.23; N, 8.80. Found: C, 64.30; H, 8.48; N, 8.71. Mp: 155-157°C.
17. Goodson, F. E.; Wallow, T. I.; Novak, B. N. J. Am. Chem. Soc. 1997, 119, 12441-12453.
18. Blank run omitting 1 showed no isomerization of the bromide under these conditions.
19. Bis-amide is the expected result of silycarbamoylation of an electrophilically substituted acetylene; see: Cunico, R. F. Tetrahedron Lett. 2001, 42, 2931-2932.
20. For the aminocarbonylation of a terminal acetylene, see: Gabriele, B.; Salerno, G.; Veltri, L.; Costa, M. J. Organomet. Chem. 2001, 622, 84-88.
21. A carbamoylsilane has previously exhibited carbene-like behavior. See: Cunico, R. F. Tetrahedron Lett. 2001, 42, 2931-2932.
22. 6): δ 185.9, 41.6, 37.3, 0.76.
23. 6): δ 185.9, 41.6, 37.3, 0.76.
24. Sulfur has been previously used to capture nucleophilic carbenes. See: (a) Nakayama, J.; Sugiura, H.; Hoshino, M. Tetrahedron Lett. 1983, 24, 2585-2588. (b) Balli, H.; Grüner, H.; Maul, R.; Schepp, H. Helv. Chim. Acta 1981, 64, 648-656. (c) Reiffen, M.; Hoffmann, R. W. Chem. Ber. 1977, 110, 37-48.
25. Sulfur has been previously used to capture nucleophilic carbenes. See: (a) Nakayama, J.; Sugiura, H.; Hoshino, M. Tetrahedron Lett. 1983, 24, 2585-2588. (b) Balli, H.; Grüner, H.; Maul, R.; Schepp, H. Helv. Chim. Acta 1981, 64, 648-656. (c) Reiffen, M.; Hoffmann, R. W. Chem. Ber. 1977, 110, 37-48.
26. Sulfur has been previously used to capture nucleophilic carbenes. See: (a) Nakayama, J.; Sugiura, H.; Hoshino, M. Tetrahedron Lett. 1983, 24, 2585-2588. (b) Balli, H.; Grüner, H.; Maul, R.; Schepp, H. Helv. Chim. Acta 1981, 64, 648-656. (c) Reiffen, M.; Hoffmann, R. W. Chem. Ber. 1977, 110, 37-48.
27. No rearranged product is obtained from the terminal halides of runs 11-14, Table 1. Factors that would favor migration in the structures of runs 7-10 are increased steric compression at the acylpalladium stage and retained conjugation in the palladium carbene intermediate.
28. Although shown as fully L-coordinated in Scheme 1, the Pd in the species undergoing loss of TMSX must to some extent become coordinatively unsaturated during this process. A longer residence time in this state may be a factor in favoring rearrangement to the intramolecularly complexed Pd carbene. In this regard, it would be significant that more cine product results from the use of catalyst B, in which the bulky tris(tert-butyl)-phosphine ligand affords a Pd(0) complex of low coordination number.
29. (a) Quayle, P.; Wang, J.; Xu, J.; Urch, C. J. Tetrahedron Lett. 1998, 39, 489-492.
30. (b) Farina, V.; Hossain, M. A. Tetrahedron Lett. 1996, 37, 6997-7000.
31. (a) Heck addition of RPdX to the vinylstannane to form an α-Pd stannane,
32. (b) loss of SnX to form the Pd(0) carbene,
33. (c) 1,3-migration of H to Pd, and
34. (d) reductive elimination to the cine alkene. Busacca, C. A.; Swestock, J.; Johnson, R. E.; Bailey, T. R.; Musza, L.; Rodger, C. A. J. Org. Chem. 1994, 59, 7553-7556.
35. Chen, S.-H. Tetrahedron Lett. 1997, 38, 4741-4744.