Unusual hydroxyl effect on fulvene endoperoxide decompositions

TETRAHEDRON LETTERS

卷:57

Article

Erden, Ihsan¹  Basada, John¹  Poli, Daniela¹  Cabrera, Gabriel¹  Xu, Fupei¹  Gronert, Scott² 

[1] San Francisco State Univ, Dept Chem & Biochem, 1600 Holloway Ave, San Francisco, CA 94132 USA

[2] Virginia Commonwealth Univ, Dept Chem, 1001 West Main St, Richmond, VA 23284 USA

关键词: Fulvenes;    Endoperoxides;    Allene oxides;    Cyclopropanones;    Oxy-allyl;   

DOI  :  10.1016/j.tetlet.2016.04.024

来源: Elsevier

【 摘 要 】

The thermal decomposition of fulvene endoperoxides ordinarily proceeds via an allene oxide intermediate affording oxepin-2(3H)-one derivatives. We have now uncovered new, unusual pathways in these decompositions where the presence of a hydroxyl group on the alkyl or aryl attached to the fulvene exocyclic double bond has a profound effect on the fate of the reactive intermediates derived from the unstable endoperoxides. Computational work supports the proposed mechanistic pathways. (C) 2016 Elsevier Ltd. All rights reserved.

【 授权许可】

Free