On the mechanism of nucleophilic substitution of allenyl(aryl)iodine(III): Formation of propargyl cation and competition with sigmatropic rearrangement

Tetrahedron Letters

Volumn 39, Issue 34, 1998, Pages 6207-6210

  Ochiai, Masahito ^a   Kida, Michio ^a   Okuyama, Tadashi ^b  

^a UNIVERSITY OF TOKUSHIMA   (Japan)

^b OSAKA UNIVERSITY   (Japan)

Author keywords

Carbenium ions; Hypervalent elements; Rearrangements; Substitution

Indexed keywords

CATION; IODINE DERIVATIVE; POLYCYCLIC AROMATIC HYDROCARBON DERIVATIVE; SILANE DERIVATIVE;

ALGORITHM; ARTICLE; MOLECULAR DYNAMICS; REACTION ANALYSIS; SYNTHESIS;

EID: 0032552128     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4039(98)01276-3     Document Type: Article

References (22)

1. [1] (a) Ochiai, M.; Ito, T.; Takaoka, Y.; Masaki, Y. J. Am. Chem. Soc. 1991, 113, 1319.
2. (b) Ochiai, M.; Ito, T.; Masakj, Y. J. Chem. Soc., Chem. Commun. 1992, 15.
3. (c) Ochiai, M.; Ito, T. J. Org. Chem. 1995, 60, 2274.
4. (d) Gately, D. A.; Luther, T. A.; Norton, J. R.; Miller, M. M.; Andersen, O. P. J. Org. Chem. 1992, 57, 6496.
5. [2] Kida, M.; Sueda, T.; Goto, S.; Okuyama, T.; Ochiai, M. J. Chem. Soc., Chem. Commun. 1996, 1933.
6. [3] Okuyama, T.; Takino, T.; Sueda, T.; Ochiai, M. J. Am. Chem. Soc. 1995, 117, 3360.
7. [4] The rearranged ortho-propargyliodobenzene undergoes further oxidation at the benzylic position under the reaction conditions to give the conjugated ynone, as shown below [5]. (equation presented)
8. [5] Ochiai, M.; Kunishima, M.; Sumi, K.; Nagao, Y.; Fujita, E. Tetrahedron Lett. 1985, 26, 4501.
9. [6] Similar substituent effects of aryliodanes 1 on the product ratios were observed for the reaction with 2b in methanol.
10. 11) in allenyl(aryl)iodine(III) 3 will presumably increase the rate of the [3,3] sigmatropic rearrangement yielding 4 and 5, compared to the unsubstituted 3 (R = H).
11. [8] (a) Jolidon, S.; Hansen, H.-J. Helv. Chim. Acta 1977, 60, 978.
12. (b)Barmettler, P.; Hansen, H.-J. Helv. Chim. Acta 1990, 73, 1515.
13. (c) Harfenist, M.; Thom, E. J. Org. Chem. 1972, 37, 841.
14. N1 reaction of 3 will exhibit a greater dependence on the nature of substituents as compared to the [3,3] sigmatropic rearrangement. For substituent effects in the thermal aromatic Claisen rearrangement of prop-2-enyl arylethers, see: (a) White, W. N.; Gwynn, D.; Schlitt, R.; Girard, C.; Fife, W. J. Am. Chem. Soc. 1958, 80, 3271.
15. (b)Goering, H. L.; Jacobson, R. R. J. Am. Chem. Soc. 1958, 80, 3277.
16. [10] Hammond, G. S. J. Am. Chem. Soc. 1955, 77, 3334.
17. [11] Schadt, F. L.; Bentley, T. W.; Schleyer, P. v. R. J. Am. Chem. Soc. 1976, 98, 7667.
18. [12] Kevill, D. N.; Anderson, S. W. J. Am. Chem. Soc. 1986, 108, 1579.
19. N1 reaction.
20. [14] For solvent effects on Claisen rearrangement in protic media, see: (a) Gajewski, J. J. Acc. Chem. Res. 1997, 30, 219.
21. (b) Ganem, B. Angew. Chem. Int. Ed. Engl. 1996, 35, 936,
22. (c) Severance, D. L.; Jorgensen, W. L. J. Am. Chem. Soc. 1992, 114, 10966.