A domino reaction for generating β-aryl aldehydes from alkynes by substrate recognition catalysis
| Autor: | F. F. Bauer, Weiwei Fang, Bernhard Breit, Yaxi Dong |
|---|---|
| Jazyk: | angličtina |
| Rok vydání: | 2019 |
| Předmět: |
Decarboxylation
Science Supramolecular chemistry General Physics and Astronomy Homogeneous catalysis Synthetic chemistry methodology 010402 general chemistry 01 natural sciences General Biochemistry Genetics and Molecular Biology Article Catalysis Cascade reaction Nucleophile lcsh:Science Multidisciplinary 010405 organic chemistry Chemistry Catalytic mechanisms Dynamic combinatorial chemistry General Chemistry Combinatorial chemistry 0104 chemical sciences lcsh:Q Supramolecular catalysis Hydroformylation |
| Zdroj: | Nature Communications, Vol 10, Iss 1, Pp 1-9 (2019) Nature Communications |
| ISSN: | 2041-1723 |
| Popis: | The development of universal catalyst systems that enable efficient, selective, and straightforward chemical transformations is of immense scientific importance. Here we develop a domino process comprising three consecutive reaction steps based on the strategy of supramolecular substrate recognition. This approach provides valuable β-aryl aldehydes from readily accessible α-alkynoic acids and arenes under mild reaction conditions, employing a supramolecular Rh catalyst containing an acylguanidine-bearing phosphine ligand. Furthermore, the synthesis of a key intermediate of Avitriptan using this protocol is accomplished. The first step of the reaction sequence is proved to be the regioselective hydroformylation of α-alkynoic acids. Remarkably, molecular recognition of the ligand and the substrate via hydrogen bonding plays a key role in this step. Control experiments indicate that the reaction further proceeds via 1,4-addition of an arene nucleophile to the unsaturated aldehyde intermediate and subsequent decarboxylation. Supramolecular interactions may be responsible for higher degree of efficiency and selectivity in homogeneous catalysis. Here, the authors exploit the concept of supramolecular catalysis to develop a domino rhodium-catalyzed hydroformylation of α-alkynoic acids followed by Michael addition of nucleophiles. |
| Databáze: | OpenAIRE |
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