Rhodium-Catalyzed Highly Regio- and Enantioselective Reductive Cyclization of Alkyne-Tethered Cyclohexadienones
| Autor: | Sangeetha Donikela, Krishna Kumar Gollapelli, Nemali Manjula, Rambabu Chegondi |
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| Rok vydání: | 2018 |
| Předmět: |
chemistry.chemical_classification
Bicyclic molecule 010405 organic chemistry Asymmetric hydrogenation Enantioselective synthesis Alkyne Regioselectivity General Chemistry 010402 general chemistry 01 natural sciences Combinatorial chemistry Desymmetrization Catalysis 0104 chemical sciences chemistry Intramolecular force |
| Zdroj: | ACS Catalysis. 8:1440-1447 |
| ISSN: | 2155-5435 |
| DOI: | 10.1021/acscatal.7b04054 |
| Popis: | Rhodium-catalyzed asymmetric hydrogenation of alkyne-tethered cyclohexadienones enables highly regio- and enantioselective reductive cyclization to afford cis-hydrobenzofurans and cis-hydroindoles in high yields. Desymmetrization of 1,3-diyne-tethered cyclohexadienones was also explored, wherein the intramolecular coordination of a Rh complex with the cyclohexadienone ring induces exclusive regioselectivity. Mechanistic studies including hydrogen–deuterium crossover experiments suggested that hydrogen activation is the rate-determining step for tandem reductive cyclization. Moreover, this highly practical and atom-economical transformation has tolerance to many functional groups with a broad range of substrate scope, allowing further transformations to expand the structural complexity of the bicyclic scaffolds. |
| Databáze: | OpenAIRE |
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