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Krasutsky PA, Kolomitsyn IV, Kiprof P, et al. A consecutive double-Criegee rearrangement using TFPAA: stepwise conversion of homoadamantane to oxahomoadamantanes. J Org Chem. 2001;66(5):1701-7doi: 10.1021/jo001219z.
Krasutsky, P. A., Kolomitsyn, I. V., Kiprof, P., Carlson, R. M., Sydorenko, N. A., & Fokin, A. A. (2001). A consecutive double-Criegee rearrangement using TFPAA: stepwise conversion of homoadamantane to oxahomoadamantanes. The Journal of organic chemistry, 66(5), 1701-7. https://doi.org/10.1021/jo001219z
Krasutsky, P A, et al. "A consecutive double-Criegee rearrangement using TFPAA: stepwise conversion of homoadamantane to oxahomoadamantanes." The Journal of organic chemistry vol. 66,5 (2001): 1701-7. doi: https://doi.org/10.1021/jo001219z
Krasutsky PA, Kolomitsyn IV, Kiprof P, Carlson RM, Sydorenko NA, Fokin AA. A consecutive double-Criegee rearrangement using TFPAA: stepwise conversion of homoadamantane to oxahomoadamantanes. J Org Chem. 2001 Mar 09;66(5):1701-7. doi: 10.1021/jo001219z. PMID: 11262116.
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J Org Chem. 2001 Mar 09;66(5):1701-7. doi: 10.1021/jo001219z.

A consecutive double-Criegee rearrangement using TFPAA: stepwise conversion of homoadamantane to oxahomoadamantanes.

The Journal of organic chemistry

P A Krasutsky, I V Kolomitsyn, P Kiprof, R M Carlson, N A Sydorenko, A A Fokin

Affiliations

  1. Natural Resources Research Institute, 5013 Miller Trunk Highway, Duluth, MN 55811-1442, USA. [email protected]

PMID: 11262116 DOI: 10.1021/jo001219z

Abstract

Rearrangement of 4-methylhomoadamantan-4-ol (1) with trifluoroperacetic acid (TFPAA) in trifluoroacetic acid (TFAA) proceeds with the formation of 4-oxahomoadamantane 6 and its derivatives (4 and 5). 2-exo-Hydroxy-4-oxahomoadamantane (5) and 6 were identified as a result of consecutive O-insertion Criegee rearrangement processes. The absence of methyl trifluoroacetate and methyl trifluoroperacetate among the reaction products, as well as the presence of acetyltrifluoroacetyl peroxide, is consistent with a double rather that a triple oxygen insertion during the course of the Criegee reaction. A mechanism involving initial Criegee rearrangement followed by a Baeyer-Villiger reaction is also excluded by kinetic considerations. The parallel formation of 4-ethyl-3-oxahomoadamantan-2-one (4) was determined to be the result of 4-methylhomoadmantan-4-ol (3) dehydration, with subsequent epoxidation of 4-methylhomoadamant-4-ene (32) to 4,5-epoxy-4-methylhomoadamantane (33), acid-catalyzed isomerization of 33 to 3-methylhomoadamantan-2-one (34), and Baeyer-Villiger oxidation to 3-methyl-5-oxabishomoadamantan-6-one (35). This sequence of reactions was followed by the acid-catalyzed isomerization to the final product 4. The proposed mechanisms for these transformations are discussed on the basis of model experiments and supporting density functional theory (DFT) calculations.

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