Stereodivergent Synthesis of the C1-C9 Tetrahydropyran Subunit of Zincophorin and Isomers Thereof

Abstract Zincophorin C1-C9 fragment and seven tetrahydropyran analogues were prepared diastereoselectively by sequential iodo­etherification and radical hydrogen-transfer reactions. Stereoselective formation of 3,7-TRANS or 3,7-CIS rings was rationalized through minimization of allylic-1,3 strain in...

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Bibliographic Details
Published in:Synthesis (Stuttgart) 2012-02, Vol.44 (3), p.474-488
Main Authors: Godin, François, Katsoulis, Ioannis, Fiola-Masson, Émilie, Dhambri, Sabrina, Mochirian, Philippe, Guindon, Yvan
Format: Article
Language:English
Subjects:
Chemistry
Exact sciences and technology
Free radicals chemistry
Heterocyclic compounds
Heterocyclic compounds with o, s, se, te hetero atom and condensed derivatives
Organic chemistry
Preparations and properties
Reactivity and mechanisms
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Summary:Abstract Zincophorin C1-C9 fragment and seven tetrahydropyran analogues were prepared diastereoselectively by sequential iodo­etherification and radical hydrogen-transfer reactions. Stereoselective formation of 3,7-TRANS or 3,7-CIS rings was rationalized through minimization of allylic-1,3 strain in chair-like transition states. Subsequent hydrogen-transfer provided 7,8-ANTI or 7,8-SYN isomers under acyclic stereocontrol or endocyclic control respectively. The latter approach relies on the formation of a [4.4.0] bicyclic complexes resulting from the chelation of the oxygen of the tetrahydropyran ring and the ester by a bidentate Lewis acid.
ISSN:0039-7881
1437-210X
DOI:10.1055/s-0031-1289661