Directing the Activation of Donor-Acceptor Cyclopropanes Towards Stereoselective 1,3-Dipolar Cycloaddition Reactions by Brønsted Base Catalysis
| Autor: | Karl Anker Jørgensen, Jakob Blom, Marc V. Iversen, Julie Jørgensen, Casper L. Barløse, Kamilla S. Jessen, Andreu Vidal-Albalat |
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| Rok vydání: | 2017 |
| Předmět: |
Stereochemistry
010405 organic chemistry small ring compounds General Chemistry General Medicine 010402 general chemistry Brønsted base Combinatorial chemistry 01 natural sciences Catalysis Cycloaddition Cyclopropane Stereocenter 0104 chemical sciences chemistry.chemical_compound chemistry Organocatalysis 1 3-Dipolar cycloaddition enantioselectivity Stereoselectivity organocatalysis Brønsted–Lowry acid–base theory cycloaddition |
| Zdroj: | Blom, J, Vidal-Albalat, A, Jørgensen, J, Barløse, C L, Jessen, K S, Iversen, M V & Jørgensen, K A 2017, ' Directing the Activation of Donor–Acceptor Cyclopropanes Towards Stereoselective 1,3-Dipolar Cycloaddition Reactions by Brønsted Base Catalysis ', Angewandte Chemie-International Edition, vol. 56, no. 39, pp. 11831-11835 . https://doi.org/10.1002/anie.201706150 |
| ISSN: | 1521-3773 |
| DOI: | 10.1002/anie.201706150 |
| Popis: | The first stereoselective organocatalyzed [3+2] cycloaddition reaction of donor-acceptor cyclopropanes is presented. It is demonstrated that by applying an optically active bifunctional Brønsted base catalyst, racemic di-cyano cyclopropylketones can be activated to undergo a stereoselective 1,3-dipolar reaction with mono- and polysubstituted nitroolefins. The reaction affords functionalized cyclopentanes with three consecutive stereocenters in high yield and stereoselectivity. Based on the stereochemical outcome, a mechanism in which the organocatalyst activates both the donor-acceptor cyclopropane and nitroolefin is proposed. Finally, chemoselective transformations of the cycloaddition products are demonstrated. |
| Databáze: | OpenAIRE |
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