On the role of triflic acid in the metal triflate-catalysed acylation of alcohols

Tetrahedron Letters

Volumn 45, Issue 4, 2004, Pages 825-829

  Dumeunier, Raphaël ^a   Markó, István E ^a  

^a Faculte des Sciences   (Belgium)

Author keywords

Acylation; Metal triflate; Triflic acid

Indexed keywords

ACID ANHYDRIDE; ALCOHOL; ESTER DERIVATIVE; METAL; TRIFLUOROMETHANESULFONIC ACID;

ACYLATION; ARTICLE; CATALYSIS; CHEMICAL PROCEDURES; REACTION ANALYSIS;

EID: 0348048819     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/j.tetlet.2003.11.034     Document Type: Article

References (37)

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14. Fujiwara K., Murai A., Yamashita M.-Y., Yasumoto T. J. Am. Chem. Soc. 120:1998;10770-10771 Paquette L.A., Barriault L., Pissarnitski D. J. Am. Chem. Soc. 121:1999;4542-4543 White J.D., Blakemore P.R., Browder C.C., Hong J., Lincoln C.M., Nagornyy P.A., Robarge L.A., Wardrop D.J. J. Am. Chem. Soc. 123:2001;8593-8595.
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17. See, for example: Keck G.E., Savin K.A., Weglarz M.A. J. Org. Chem. 60:1995;3194-3204.
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19. a studies, see: Castellani C.B., Carugo O., Giusti M., Leopizzi C., Perotti A., Invernizzi A.G., Vidari G. Tetrahedron. 52:1996;11045-11052.
20. Balaban T.S., Unuta C., Gheorghiu M.O., Balaban A.T. Tetrahedron Lett. 26:1985;4669-4672 Brown H.C., Kanner B. J. Am. Chem. Soc. 88:1966;986-992 Brown H.C., Kanner B. J. Am. Chem. Soc. 75:1953;3865.
21. Balaban T.S., Unuta C., Gheorghiu M.O., Balaban A.T. Tetrahedron Lett. 26:1985;4669-4672 Brown H.C., Kanner B. J. Am. Chem. Soc. 88:1966;986-992 Brown H.C., Kanner B. J. Am. Chem. Soc. 75:1953;3865.
22. Balaban T.S., Unuta C., Gheorghiu M.O., Balaban A.T. Tetrahedron Lett. 26:1985;4669-4672 Brown H.C., Kanner B. J. Am. Chem. Soc. 88:1966;986-992 Brown H.C., Kanner B. J. Am. Chem. Soc. 75:1953;3865.
23. Since up to three equivalents of triflic acid could theoretically be generated per metal triflate, we have decided to use a 1:3 ratio of metal complex/DTBMP. However, even one equivalent of the hindered base is sufficient to significantly reduce the rate of these acylation reactions (Table 2, entry 5).
24. Competitive elimination has also been observed in the metal triflate acylation of several allylic and tertiary alcohols (see Refs. [2a,2g,2i,2j]).
25. 2O/TfOH) was deduced from the ratio of acylated adduct versus elimination product.
26. Triflic acid has been used, and sometimes demonstrated to be the active species, in several catalytic processes: Kotsuki H., Arimura K., Ohishi T., Maruzasa R. J. Org. Chem. 64:1999;3770-3773 Kotsuki H., Ohishi T., Inoue M., Kojima T. Synthesis. 1999;603-606 Kotsuki H., Arimura K., Araki T., Shinohara T. Synlett. 1999;462-464 Répichet S., Le Roux C., Dubac J., Desmurs J.-R. Eur. J. Org. Chem. 1998;2743-2746 Laurent-Robert H., Le Roux C., Dubac J. Synlett. 1998;1138-1140 (f) Tsuchimoto T., Tobita K., Hiyama T., Fukuzawa S.-I. J. Org. Chem. 62:1997;6997-7005. see also Ref. [2g].
27. Triflic acid has been used, and sometimes demonstrated to be the active species, in several catalytic processes: Kotsuki H., Arimura K., Ohishi T., Maruzasa R. J. Org. Chem. 64:1999;3770-3773 Kotsuki H., Ohishi T., Inoue M., Kojima T. Synthesis. 1999;603-606 Kotsuki H., Arimura K., Araki T., Shinohara T. Synlett. 1999;462-464 Répichet S., Le Roux C., Dubac J., Desmurs J.-R. Eur. J. Org. Chem. 1998;2743-2746 Laurent-Robert H., Le Roux C., Dubac J. Synlett. 1998;1138-1140 (f) Tsuchimoto T., Tobita K., Hiyama T., Fukuzawa S.-I. J. Org. Chem. 62:1997;6997-7005. see also Ref. [2g].
28. Triflic acid has been used, and sometimes demonstrated to be the active species, in several catalytic processes: Kotsuki H., Arimura K., Ohishi T., Maruzasa R. J. Org. Chem. 64:1999;3770-3773 Kotsuki H., Ohishi T., Inoue M., Kojima T. Synthesis. 1999;603-606 Kotsuki H., Arimura K., Araki T., Shinohara T. Synlett. 1999;462-464 Répichet S., Le Roux C., Dubac J., Desmurs J.-R. Eur. J. Org. Chem. 1998;2743-2746 Laurent-Robert H., Le Roux C., Dubac J. Synlett. 1998;1138-1140 (f) Tsuchimoto T., Tobita K., Hiyama T., Fukuzawa S.-I. J. Org. Chem. 62:1997;6997-7005. see also Ref. [2g].
29. Triflic acid has been used, and sometimes demonstrated to be the active species, in several catalytic processes: Kotsuki H., Arimura K., Ohishi T., Maruzasa R. J. Org. Chem. 64:1999;3770-3773 Kotsuki H., Ohishi T., Inoue M., Kojima T. Synthesis. 1999;603-606 Kotsuki H., Arimura K., Araki T., Shinohara T. Synlett. 1999;462-464 Répichet S., Le Roux C., Dubac J., Desmurs J.-R. Eur. J. Org. Chem. 1998;2743-2746 Laurent-Robert H., Le Roux C., Dubac J. Synlett. 1998;1138-1140 (f) Tsuchimoto T., Tobita K., Hiyama T., Fukuzawa S.-I. J. Org. Chem. 62:1997;6997-7005. see also Ref. [2g].
30. Triflic acid has been used, and sometimes demonstrated to be the active species, in several catalytic processes: Kotsuki H., Arimura K., Ohishi T., Maruzasa R. J. Org. Chem. 64:1999;3770-3773 Kotsuki H., Ohishi T., Inoue M., Kojima T. Synthesis. 1999;603-606 Kotsuki H., Arimura K., Araki T., Shinohara T. Synlett. 1999;462-464 Répichet S., Le Roux C., Dubac J., Desmurs J.-R. Eur. J. Org. Chem. 1998;2743-2746 Laurent-Robert H., Le Roux C., Dubac J. Synlett. 1998;1138-1140 (f) Tsuchimoto T., Tobita K., Hiyama T., Fukuzawa S.-I. J. Org. Chem. 62:1997;6997-7005. see also Ref. [2g].
31. Triflic acid has been used, and sometimes demonstrated to be the active species, in several catalytic processes: Kotsuki H., Arimura K., Ohishi T., Maruzasa R. J. Org. Chem. 64:1999;3770-3773 Kotsuki H., Ohishi T., Inoue M., Kojima T. Synthesis. 1999;603-606 Kotsuki H., Arimura K., Araki T., Shinohara T. Synlett. 1999;462-464 Répichet S., Le Roux C., Dubac J., Desmurs J.-R. Eur. J. Org. Chem. 1998;2743-2746 Laurent-Robert H., Le Roux C., Dubac J. Synlett. 1998;1138-1140 (f) Tsuchimoto T., Tobita K., Hiyama T., Fukuzawa S.-I. J. Org. Chem. 62:1997;6997-7005. see also Ref. [2g].
32. For reasons of clarity, only one benzoate is shown on the metal. However, it is quite possible that several species, formed by the exchange of one, two or three triflate ligands might be involved in these catalytic processes.
33. For a catalytic version of the Friedel-Crafts acylation using triflic acid and proceeding via the acyl triflate intermediate, see: Effenberger F., Epple G. Angew. Chem., Int. Ed. 11:1972;300.
34. Brown L., Koreeda M. J. Org. Chem. 49:1984;3875-3880.
35. As with TfOH, a second aliquot of 12 (7 mol %) had to be added after 18 h to reach full completion.
36. It is important to note that the triflate salt of DTBMP does not catalyse the acylation reaction.
37. 2 are poorly active. Indeed, if only one triflate is exchanged, the maximum yield of acetate 18 should be 33%.