New Catalysts for the Base-Promoted Isomerization of Epoxides to Allylic Alcohols. Broadened Scope and Near-Perfect Asymmetric Induction

Optically active (1S,3R,4R)-3-[N-(trans-2,5-dialkyl)pyrrolidinyl]methyl-2-azabicyclo-[2.2.1]heptanes were evaluated as catalysts for the enantioselective β-elimination of meso-epoxides. The (2R,5R)-dimethylpyrrolidinyl-substituted catalyst 4 exhibited exceptionally high enantioselectivity and reacti...

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Veröffentlicht in:	Journal of organic chemistry 2002-03, Vol.67 (5), p.1567-1573
Hauptverfasser:	Bertilsson, Sophie K, Södergren, Mikael J, Andersson, Pher G
Format:	Artikel
Sprache:	eng
Schlagworte:	Catalysis Catalysts: preparations and properties Chemistry Exact sciences and technology General and physical chemistry Heterocyclic compounds Heterocyclic compounds with only one n hetero atom and condensed derivatives Organic chemistry Preparations and properties Theory of reactions, general kinetics. Catalysis. Nomenclature, chemical documentation, computer chemistry
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Zusammenfassung:	Optically active (1S,3R,4R)-3-[N-(trans-2,5-dialkyl)pyrrolidinyl]methyl-2-azabicyclo-[2.2.1]heptanes were evaluated as catalysts for the enantioselective β-elimination of meso-epoxides. The (2R,5R)-dimethylpyrrolidinyl-substituted catalyst 4 exhibited exceptionally high enantioselectivity and reactivity, and several substrates were rearranged with enantioselectivities of 98−99% ee. In addition, the use of 4 allowed the first successful, true catalytic rearrangement of the difficult substrates cyclopentene oxide (81%, 96% ee) and (Z)-4-octene oxide (80%, 91% ee).
ISSN:	0022-3263 1520-6904
DOI:	10.1021/jo010934l