Palladium-Catalyzed Formal (3 + 2) Cycloaddition Reactions of 2-Nitro-1,3-enynes with Vinylaziridines, -epoxides, and -cyclopropanes
| Autor: | Andrew J. Tague, Christopher Richardson, Melanie A. Drew, Stephen G. Pyne, Christopher J. T. Hyland |
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| Rok vydání: | 2021 |
| Předmět: |
010405 organic chemistry
Chemistry Organic Chemistry Diastereomer chemistry.chemical_element 010402 general chemistry 01 natural sciences Biochemistry Medicinal chemistry Cycloaddition 0104 chemical sciences Catalysis Elimination reaction Alkane stereochemistry Nitro Physical and Theoretical Chemistry Single crystal Palladium |
| Zdroj: | Organic Letters. 23:4635-4639 |
| ISSN: | 1523-7052 1523-7060 |
| DOI: | 10.1021/acs.orglett.1c01364 |
| Popis: | A two-step Pd-catalyzed (3 + 2) cycloaddition/HNO2 elimination reaction sequence has been developed to give novel cyclic 1,3-dien-5-yne systems from Pd-stabilized zwitterionic 1,3-dipoles and 2-nitro-1,3-enyne substrates. The process is highly atom-efficient and tolerates the reaction of 2-vinyloxirane, 1-tosyl-2-vinylaziridine, and diethyl 2-vinylcyclopropane-1,1-dicarboxylate derived 1,3-dipoles with a variety of 2-nitro-1,3-enyne substrates. The stereochemistry of the intermediate (3 + 2) cycloadducts was determined by single crystal X-ray analysis. Furthermore, a selective kinetic elimination of the cycloadduct with an antiperiplanar relationship between the NO2 group and the participating hydrogen was demonstrated, allowing for efficient isolation of a single diastereoisomer of the cycloadduct. |
| Databáze: | OpenAIRE |
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