Synthesis of fused tricyclic systems by thermal cope rearrangement of furan-substituted vinyl cyclopropanes

Klaus, V., Wittmann, S., Senn, H. M. and Clark, J. S. (2018) Synthesis of fused tricyclic systems by thermal cope rearrangement of furan-substituted vinyl cyclopropanes. Organic and Biomolecular Chemistry, 16(21), pp. 3970-3982. (doi: 10.1039/C8OB00924D) (PMID:29761822)

Abstract

A novel method for the stereoselective construction of hexahydroazuleno[4,5-b]furans from simple precursors has been developed. The route involves the use of our recently developed Brønsted acid catalysed cyclisation reaction of acyclic ynenones to prepare fused 1-furanyl-2-alkenylcyclopropanes that undergo highly stereoselective thermal Cope rearrangement to produce fused tricyclic products. Substrates possessing an E-alkene undergo smooth Cope rearrangement at 40 °C, whereas the corresponding Z-isomers do not react at this temperature. Computational studies have been performed to explain the difference in behaviour of the E- and Z-isomers in the Cope rearrangement reaction. The hexahydroazuleno[4,5-b]furans produced by Cope rearrangement have potential as advanced intermediates for the synthesis of members of the guaianolide family of natural products.

• Item Type: Articles
• Additional Information: The authors thank the University of Glasgow for studentship funding for VK and a postdoctoral fellowship for SW.
• Status: Published
• Refereed: Yes
• Glasgow Author(s) Enlighten ID: Clark, Professor Stephen and Wittmann, Mr Stephane and Senn, Dr Hans and Klaus, Verena
• Authors: Klaus, V., Wittmann, S., Senn, H. M., and Clark, J. S.
• College/School: College of Science and Engineering > School of Chemistry
• Journal Name: Organic and Biomolecular Chemistry
• Publisher: Royal Society of Chemistry
• ISSN: 1477-0520
• ISSN (Online): 1477-0539
• Published Online: 15 May 2018
• Copyright Holders: Copyright © 2018 The Royal Society of Chemistry
• First Published: First published in Organic and Biomolecular Chemistry 16(21): 3970-3982
• Publisher Policy: Reproduced under a Creative Commons License