Strain‐Induced Nucleophilic Ring Opening of Donor–Acceptor Cyclopropenes for Synthesis of Monosubstituted Succinic Acid Derivatives
| Autor: | Kan Wang, Jinzhou Chen, Michael P. Doyle, Jinping Lei, Kuiyong Dong, Kostiantyn O. Marichev, Nicole Greco |
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| Rok vydání: | 2020 |
| Předmět: |
Cyclopropanes
010405 organic chemistry Chemistry Organic Chemistry Succinic Acid Succinates General Chemistry 010402 general chemistry Ring (chemistry) 01 natural sciences Medicinal chemistry Catalysis 0104 chemical sciences Ring strain Metal chemistry.chemical_compound Nucleophile Succinic acid visual_art visual_art.visual_art_medium Carboxylate Amines Carbene |
| Zdroj: | Chemistry – A European Journal. 27:340-347 |
| ISSN: | 1521-3765 0947-6539 |
| DOI: | 10.1002/chem.202003427 |
| Popis: | 1,2,3-Trisubstituted donor-acceptor cyclopropenes (DACPs) generated in situ from enoldiazo compounds react with nucleophiles to form α-substituted succinic acid derivatives in high yields. Initial dirhodium(II) carboxylate catalysis rapidly converts enoldiazo-acetates or -acetamides to DACPs that undergo catalyst-free Favorskii ring opening with amines, and also with anilines, alcohols, and thiols, when facilitated by catalytic amounts of 4-dimethylaminopyridine (DMAP). This methodology provides easy access to mixed esters and amides of monosubstituted succinic acids, including derivatives of naturally occurring compounds. It also affords dihydrazide, dihydroxamic acid, and diamide derivatives, as well as α-substituted tetrahydropyridazine-3,6-diones in high yields. Attempts to generate optically enriched DACPs were not successful because their populations having the R and S configurations formed with a chiral dirhodium catalyst are quite similar, and the loss of enantiocontrol likely originates from the DACP ring forming step which is reversible with its intermediate metal carbene. |
| Databáze: | OpenAIRE |
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