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Metal‐Catalyzed Cycloetherification Reactions of β,γ‐ and γ,δ‐Allendiols: Chemo‐, Regio‐, and Stereocontrol in the Synthesis of Oxacycles
Author(s) -
Alcaide Benito,
Almendros Pedro,
Carrascosa Rocío,
Martínez del Campo Teresa
Publication year - 2010
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.201001520
Subject(s) - enantiopure drug , catalysis , metal , chemistry , carbon atom , medicinal chemistry , stereoselectivity , stereochemistry , combinatorial chemistry , organic chemistry , enantioselective synthesis , ring (chemistry)
Versatile routes that lead to a variety of functionalized enantiopure tetrahydrofurans, dihydropyrans, and tetrahydrooxepines are based on chemo‐, regio‐, and stereocontrolled metal‐catalyzed oxycyclization reactions of β,γ‐ and γ,δ‐allendiols, which were readily prepared from ( R )‐2,3‐ O ‐isopropylideneglyceraldehyde. The application of Pd II , Pt II , Au III , or La III salts as the catalysts gives controlled access to differently sized oxacycles in enantiopure form. Usually, chemoselective cyclization reactions occurred exclusively by attack of the secondary hydroxy group (except for the oxybromination of phenyl β,γ‐allenic diols 3 b and 3 d ) to an allenic carbon atom. Regio‐ and stereocontrol issues are mainly influenced by the nature of the metal catalysts and substituents.