Hyperconjomer stereocontrol of cationic polyene cyclisations. Issue 37 (17th September 2019)

• Record Type: Journal Article
• Authors: Rodger, Robert T.; Graham, Marlowe S.; McErlean, Christopher S. P.
• Is Part Of: Organic & biomolecular chemistry. Volume 17:Issue 37(2019)
• Page Start: 8551
• Page End: 8560
• Publication Date: 2019-09-17
• Subjects: Chemistry, Organic -- Periodicals; Bioorganic chemistry -- Periodicals; Chemistry, Physical organic -- Periodicals; 547
• DOI: 10.1039/c9ob01364d
• Languages: English
• ISSNs: 1477-0520

Abstract

Abstract : The stereochemical outcome of cationic polyene cyclisations of geranylbenzene derivatives is affected by the different reactivity of hyperconjomer intermediates. The synthesis of (±)-taiwaniaquinone G by a cationic polyene cyclisation is described. Abstract : Polyene cyclisations are a powerful method for the direct generation of molecular complexity. This paper describes the use of computational methods to investigate the stereoselectivity of cationic polyene cyclisations of geranylbenzene derivatives. The outcomes highlight the different reactivity of hyperconjomers during the key Friedel–Crafts alkylation step, and informed a successful strategy for the synthesis of (±)-taiwaniaquinone G with improved levels of stereoselectivity.