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Experimental and Theoretical Studies on the Bismuth‐Triflate‐Catalysed Cycloisomerisation of 1,6,10‐Trienes and Aryl Polyenes
Author(s) -
Godeau Julien,
FontaineVive Fabien,
Antoniotti Sylvain,
Duñach Elisabet
Publication year - 2012
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201202263
Subject(s) - trifluoromethanesulfonate , catalysis , bismuth , chemistry , aryl , lewis acids and bases , molecule , medicinal chemistry , organic chemistry , computational chemistry , alkyl
Cycloisomerisation of polyenes such as diethyl geranylprenylmalonate [( E )‐ 1 a ], diethyl geranylphenylmalonate [( E )‐ 2 a ] and diethyl cinnamylgeranylmalonate [( E , E )‐ 3 a ] catalysed by bismuth triflate was studied from experimental and theoretical viewpoints. Several intermediates were isolated and characterised, and calculated transition‐state structures are proposed for the three reactions. The diastereoselectivity observed during the reaction of ( E )‐ or ( Z )‐ 2 a in favour of the formation of trans ‐fused bicyclic products is discussed in detail. The nature of the active catalytic species derived from bismuth triflate was also investigated, and the formation of a hybrid Lewis acid/Brønsted acid catalyst with water molecules is proposed, supported by experimental and theoretical data.