Synthesis of dibenz[b,f]oxepins via manganese(III)-based oxidative 1,2-radical rearrangement

Zhiqi Cong; Takumi Miki; Osamu Urakawa; Hiroshi Nishino

doi:10.1021/jo9002773

Synthesis of dibenz[b,f]oxepins via manganese(III)-based oxidative 1,2-radical rearrangement

J Org Chem. 2009 May 15;74(10):3978-81. doi: 10.1021/jo9002773.

Authors

Zhiqi Cong¹, Takumi Miki, Osamu Urakawa, Hiroshi Nishino

Affiliation

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

PMID: 19385611
DOI: 10.1021/jo9002773

Abstract

The oxidation of monoalkyl 2-(9H-xanthenyl)malonates 1 with Mn(OAc)(3) gave the 9- or 10-dibenz[b,f]oxepincarboxylates 2 in good yields. The reaction proceeds with high regioselectivity except for the case of (1-methoxyxanthenyl)malonate 1 (R(1) = Me, R(2) = 1-MeO), which gave two regioisomers. It was proposed that the process for the formation of 2 must include the 1,2-aryl radical rearrangement followed by oxidative decarboxylation.