Design of an Organocatalyst for the Enantioselective Diels−Alder Reaction with α-Acyloxyacroleins

We have realized the first enantioselective organocatalytic Diels−Alder reaction between α-substituted acroleins, such as α-acyloxyacroleins, and not only cyclic but also acyclic dienes. α-Acyloxyacroleins are useful as synthetic equivalents of α-haloacroleins. The present catalyst could be prepared...

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Bibliographic Details
Published in:Journal of the American Chemical Society 2005-08, Vol.127 (30), p.10504-10505
Main Authors: Ishihara, Kazuaki, Nakano, Kazuhiko
Format: Article
Language:English
Subjects:
Chemical reactivity
Chemistry
Exact sciences and technology
Organic chemistry
Reactivity and mechanisms
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Summary:We have realized the first enantioselective organocatalytic Diels−Alder reaction between α-substituted acroleins, such as α-acyloxyacroleins, and not only cyclic but also acyclic dienes. α-Acyloxyacroleins are useful as synthetic equivalents of α-haloacroleins. The present catalyst could be prepared in situ from pentafluorobenzenesulfonic acid (2.5−3.0 equiv) and chiral triamine (1 equiv) derived from H-l-Phe-l-Leu-N(CH2CH2)2. The enantioselective Diels−Alder reaction of 5-(benzyloxymethyl)cyclopentadiene, cyclopentadiene, cyclohexadiene, 2,3-dimethylbutadiene, and isoprene with α-(p-methoxybenzoyloxy)acrolein catalyzed by the above chiral ammonium salt (2.5−20 mol %) at −20−22 °C gave the corresponding adducts with 83, 83, 91, 92, and 88% ee, respectively.
ISSN:0002-7863
1520-5126
DOI:10.1021/ja053368a