Stereoselective Indium-Promoted Allylation of γ-Hydroxy-γ-Lactones under Aqueous Conditions. The Neighboring Carboxyl Effect

Journal of Organic Chemistry

Volumn 62, Issue 24, 1997, Pages 8284-8285

  Bernardelli, Patrick ^a   Paquette, Leo A ^a  

^a OHIO STATE UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0001015055     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo9716800     Document Type: Article

References (13)

1. (a) Li, C.-J. Chem. Rev. (Washington, D.C.) 1993, 93, 2023.
2. (b) Chan, T.-H.; Li, C.-J.; Lee, M. C.; Wei, Z. Y. Can. J. Chem. 1994, 72, 1181.
3. Lubineau, A.; Auge, J.; Queneau, Y. Synthesis 1994, 741.
4. (a) Paquette, L. A.; Mitzel, T. M. J. Am. Chem. Soc. 1996, 118, 1931.
5. (b) Paquette, L. A.; Lobben, P. C. J. Am. Chem. Soc. 1996, 118, 1917.
6. Isaac, M. B.; Paquette, L. A. J. Org. Chem. 1997, 62, 5333 and related references cited in these papers.
7. Paquette, L. A.; Mitzel, T. M.; Isaac, M. B.; Crasto, C. F.; Schomer, W. W. J. Org. Chem. 1997, 62, 4293.
8. Paquette, L. A.; Isaac, M. B. Heterocycles, in press.
9. Paquette, L. A. In Green Chemistry: Frontiers in Benign Chemical Synthesis and Processing; Anastas, P., Williamson, T., Eds.; Oxford University Press: Oxford, 1997, in press.
10. Bernardelli, P. Ph.D. Dissertation, The Ohio State University, 1997.
11. Direct exposure of the γ-menthyloxy γ-lactones to allyltrimethylsilane in the presence of trimethylsilyl triflate as recommended for dimethyl acetals (Noyori, R.; Murata, S.; Suzuki, M. Tetrahedron 1981, 37, 3899) did not result in consumption of the starting material. This lack of reactivity is attributable to the steric bulk of the menthyloxy substituent, which impedes formation of the oxonium ion.
12. Since the hydroxy acids are the presumed intermediates in this reaction, the possibility exists that cyclization to the lactone with an exo substituent may be faster than cyclization to give the lactone with an endo-allyl group. While no guarantee can be made that both hydroxy acids have completely cyclized, none were observed spectroscopically in any experiments. More importantly, the exo allyl products were invariably isolated in yields well in excess of 50% (Table 1, entries 1, 3, and 4), even when a counterbalancing chelating substituent was present (Table 1, entry 2). Consequently, the results are entirely consistent with the intervention of chelated transition states as proposed.
13. Canonne, P.; Plamondon J.; Akssira, M. Tetrahedron 1988, 44, 2903.