Rearrangement of Methylenebis(cyclohexane-1,3-dione) Enols Induced by Mn(III)-Catalyzed Aerobic Oxidation

Yûki Murakami; Kazuki Hisano; Hiroshi Nishino

doi:10.1021/acs.joc.2c00647

Rearrangement of Methylenebis(cyclohexane-1,3-dione) Enols Induced by Mn(III)-Catalyzed Aerobic Oxidation

J Org Chem. 2022 Jul 1;87(13):8782-8787. doi: 10.1021/acs.joc.2c00647. Epub 2022 Jun 21.

Authors

Yûki Murakami¹, Kazuki Hisano¹, Hiroshi Nishino¹

Affiliation

¹ Department of Chemistry, Graduate School of Science, Kumamoto University, Kurokami 2-39-1, Chûou-Ku, Kumamoto 860-8555, Japan.

PMID: 35726860
DOI: 10.1021/acs.joc.2c00647

Abstract

The Mn(III)-catalyzed aerobic oxidation of methylenebis(cyclohexane-1,3-dione) enols 1 resulted in 6a-hydroxy-2,3,4,6a,7,8,9,10a-octahydro-1H-benzo[c]chromene-1,6,10-triones 3 during the formation of 4,5,8,10,11,12-hexahydro-2H-benzo[b]oxecine-2,6,7,9(3H)-tetraones 2. The mechanism for the formation of 3 was proposed on the basis of the isolation of intermediates 2, which were transformed into 3 under Claisen and retro-Claisen conditions.