Facile Fragmentations of Alkeny1(aryl)iodonium Triflates

Journal of Organic Chemistry

Volumn 62, Issue 22, 1997, Pages 7534-7535

  Hinkle, Robert J ^a   Thomas, David B ^a  

^a The College of William and Mary   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0001405694     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo971132m     Document Type: Article

References (31)

1. Recent reviews include: Varvoglis, A. Tetrahedron 1997, 53, 1179-1255. Zhdankin, V. V.; Stang, P. J. Chem. Rev. 1996, 96, 1123-1178.
2. Recent reviews include: Varvoglis, A. Tetrahedron 1997, 53, 1179-1255. Zhdankin, V. V.; Stang, P. J. Chem. Rev. 1996, 96, 1123-1178.
3. For advances in organic synthesis, see: Varvoglis, A. Hypervalent Iodine in Organic Synthesis; Academic: New York, 1997.
4. Ochiai, M.; Sumi, K.; Takaoka, Y.; Kunishima, M.; Nagao, Y.; Shiro, M.; Fujita, E. Tetrahedron 1988, 4095-4112.
5. Hinkle, R. J.; Poulter, G. M.; Stang, P. J. J. Am. Chem. Soc. 1993, 115, 11626-11627. Moriarty, R. M.; Epa, W. R. Tetrahedron Lett. 1992, 4095-4098. Moriarty, R. M.; Epa, W. R.; Awasthi, A. K. J. Am. Chem. Soc. 1991, 113, 6315-6316.
6. Hinkle, R. J.; Poulter, G. M.; Stang, P. J. J. Am. Chem. Soc. 1993, 115, 11626-11627. Moriarty, R. M.; Epa, W. R. Tetrahedron Lett. 1992, 4095-4098. Moriarty, R. M.; Epa, W. R.; Awasthi, A. K. J. Am. Chem. Soc. 1991, 113, 6315-6316.
7. Hinkle, R. J.; Poulter, G. M.; Stang, P. J. J. Am. Chem. Soc. 1993, 115, 11626-11627. Moriarty, R. M.; Epa, W. R. Tetrahedron Lett. 1992, 4095-4098. Moriarty, R. M.; Epa, W. R.; Awasthi, A. K. J. Am. Chem. Soc. 1991, 113, 6315-6316.
8. Ochiai, M.; Shu, T.; Nagaoka, T.; Kitagawa, Y. J. Org. Chem. 1997, 62, 2130-2138.
9. Okuyama, T.; Takino, T.; Sueda, T.; Ochiai, M. J. Am. Chem. Soc. 1995, 117, 3360-3367.
10. Vinyl cations containing α-alkyl groups are a well-studied class of intermediates. See, inter alia: (a) Summerville, R. H.; Schleyer, P. v. R. J. Am. Chem. Soc. 1974, 96, 1110-1120. (b) Summerville, R. H.; Senkler, C. A.; Schleyer, P. v. R.; Dueber, T. E.; Stang, P. J. J. Am. Chem. Soc. 1974, 96, 1100-1109. (c) Stang, P. J.; Rappoport, Z.; Hanack, M.; Subramanian, L. R. Vinyl Cations; Academic: New York, 1979 and references therein.
11. Vinyl cations containing α-alkyl groups are a well-studied class of intermediates. See, inter alia: (a) Summerville, R. H.; Schleyer, P. v. R. J. Am. Chem. Soc. 1974, 96, 1110-1120. (b) Summerville, R. H.; Senkler, C. A.; Schleyer, P. v. R.; Dueber, T. E.; Stang, P. J. J. Am. Chem. Soc. 1974, 96, 1100-1109. (c) Stang, P. J.; Rappoport, Z.; Hanack, M.; Subramanian, L. R. Vinyl Cations; Academic: New York, 1979 and references therein.
12. Vinyl cations containing α-alkyl groups are a well-studied class of intermediates. See, inter alia: (a) Summerville, R. H.; Schleyer, P. v. R. J. Am. Chem. Soc. 1974, 96, 1110-1120. (b) Summerville, R. H.; Senkler, C. A.; Schleyer, P. v. R.; Dueber, T. E.; Stang, P. J. J. Am. Chem. Soc. 1974, 96, 1100-1109. (c) Stang, P. J.; Rappoport, Z.; Hanack, M.; Subramanian, L. R. Vinyl Cations; Academic: New York, 1979 and references therein.
13. For more recent references on vinyl cations, including a primary cation derived from hydration of acetylene, see: Bott, K. Chem. Ber. 1994, 127, 933-939. Lucchini, V.; Modena, G. J. Am. Chem. Soc. 1990, 112, 6291-6296.
14. For more recent references on vinyl cations, including a primary cation derived from hydration of acetylene, see: Bott, K. Chem. Ber. 1994, 127, 933-939. Lucchini, V.; Modena, G. J. Am. Chem. Soc. 1990, 112, 6291-6296.
15. For NMR studies of stabilized vinyl cations, see: Siehl, H.-U. Pure Appl. Chem. 1995, 67, 769-775. Siehl, H.-U.; Kaufmann, F.-P.; Hori, K. J. Am. Chem. Soc. 1992, 114, 9343-9349.
16. For NMR studies of stabilized vinyl cations, see: Siehl, H.-U. Pure Appl. Chem. 1995, 67, 769-775. Siehl, H.-U.; Kaufmann, F.-P.; Hori, K. J. Am. Chem. Soc. 1992, 114, 9343-9349.
17. Hinkle, R. J.; Stang, P. J. Synthesis 1994, 393-396.
18. Zhdankin, V. V.; Stang, P. J. Tetrahedron Lett. 1993, 34, 6853-6856.
19. 1H NMR spectrum, is contained in the Supporting Information.
20. Triflate 3a was synthesized by the hindered base method: Stang, P. J.; Treptow, W. Synthesis 1980, 283-284.
21. See ref 7a for the preparation of (E)-4a and (Z)-4a. Isomers were identified according to chemical shift of the vinylic protons. Also see: Stang, P. J.; Datta, A. K. J. Am. Chem. Soc. 1989, 111, 1358-1363.
22. N2 and phenonium ion reactions of vinyliodonium salts were recently reported: Okuyama, T.; Ochiai, M. J. Am. Chem. Soc. 1997, 119, 4785-4786.
23. Equilibration of some vinyl triflates to a thermodynamic mixture can be accomplished in the presence of excess triflic acid. See: ref 7b.
24. N2 mechanism. Several experiments to determine the mode of reaction are underway and will be reported in due course.
25. N-E reactions was recently published: Lucchini, V.; Modena, G.; Pasquato, L. J. Am. Chem. Soc. 1995, 117, 2297-2300.
26. For a brief report of nucleophilic substitutions of (E)-β-alkylvinyliodonium tetrafluoroborates with halides, see: Ochiai, M.; Ochima, K.; Masaki, Y. J. Am. Chem. Soc. 1991, 113, 7059-7061.
27. 1H NMR spectrum were used.
28. For detailed discussions of the factors influencing stereochemistry in the formation of (Z)- and (E)-4a, see refs 7a and 7c.
29. 24 The presence of (E)-4b strongly implies a bridging phenonium ion is involved in the rearrangement and stabilization of the primary vinyl cation.
30. Allene 7 is a known compound with distinctive spectral characteristics. For preparation via enol phosphates, see: Brummond, K. M.; Dingess, E. A.; Kent, J. L. J. Org. Chem. 1996, 61, 6096-6097.
31. Jäckel, K.-P.; Hanack, M. Chem. Ber. 1977, 110, 199-207.