A broadly applicable and practical oligomeric (salen)Co catalyst for enantioselective epoxide ring-opening reactions

The (salen)Co catalyst (4a) can be prepared as a mixture of cyclic oligomers in a short, chromatography-free synthesis from inexpensive, commercially available precursors. This catalyst displays remarkable enhancements in reactivity and enantioselectivity relative to monomeric and other multimeric (...

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Bibliographic Details
Published in:Tetrahedron 2014-07, Vol.70 (27-28), p.4165-4180
Main Authors: White, David E., Tadross, Pamela M., Lu, Zhe, Jacobsen, Eric N.
Format: Article
Language:English
Subjects:
Desymmetrization
Epoxides
Kinetic resolution
Ring-opening
Salen
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Summary:The (salen)Co catalyst (4a) can be prepared as a mixture of cyclic oligomers in a short, chromatography-free synthesis from inexpensive, commercially available precursors. This catalyst displays remarkable enhancements in reactivity and enantioselectivity relative to monomeric and other multimeric (salen)Co catalysts in a wide variety of enantioselective epoxide ring-opening reactions. The application of catalyst 4a is illustrated in the kinetic resolution of terminal epoxides by nucleophilic ring-opening with water, phenols, and primary alcohols; the desymmetrization of meso epoxides by addition of water and carbamates; and the desymmetrization of oxetanes by intramolecular ring opening with alcohols and phenols. The favorable solubility properties of complex 4a under the catalytic conditions facilitated mechanistic studies, allowing elucidation of the basis for the beneficial effect of oligomerization. Finally, a catalyst selection guide is provided to delineate the specific advantages of oligomeric catalyst 4a relative to (salen)Co monomer 1 for each reaction class. [Display omitted]
ISSN:0040-4020
1464-5416
DOI:10.1016/j.tet.2014.03.043