Stereoselectivity of the captodative alkenes 1-acetylvinyl arenecarboxylates in Diels-Alder reactions with cyclic dienes and stereospecific rearrangement of their bicyclo[2.2.n] α-ketol adducts
| Autor: | Rosa Padilla, Raul Aguilar, Miguel A. Vázquez, Daniel Zárate-Zárate, Blanca M. Santoyo, Joaquín Tamariz, Hugo A. Jiménez-Vázquez |
|---|---|
| Jazyk: | angličtina |
| Rok vydání: | 2020 |
| Předmět: |
chemistry.chemical_classification
Cyclopentadiene Bicyclic molecule Chemistry Alkene Stereochemistry General Chemical Engineering 02 engineering and technology General Chemistry 010402 general chemistry 021001 nanoscience & nanotechnology 01 natural sciences Cycloaddition 0104 chemical sciences lcsh:Chemistry chemistry.chemical_compound Stereospecificity lcsh:QD1-999 Reactivity (chemistry) Stereoselectivity 0210 nano-technology Lactone |
| Zdroj: | Arabian Journal of Chemistry, Vol 13, Iss 1, Pp 900-915 (2020) |
| ISSN: | 1878-5352 |
| Popis: | Captodative alkene 1-acetylvinyl p-nitrobenzenecarboxylate 1a was evaluated for its reactivity and stereoselectivity with cyclohexadiene (10) in Diels-Alder reactions, showing exclusive endo preference. The two hydrolyzed products of the endo and the exo adducts obtained from the Diels-Alder cycloaddition between 1a and cyclopentadiene (7) were 8b and 9b. When treated with mCPBA, a ring expansion took place to stereospecifically yield the novel 3-oxatricyclo[3.3.1.02,4]nonanone acyloins 15 and 16, respectively. In the case of the α-ketol bicyclo[2.2.2]octanes 11b and 12b, the epoxidation/Baeyer-Villiger cascade process was preferred, resulting in the syn ketoepoxide 19b from each isomer. A synthetic application of this kind of transformation was carried out by reacting ketols 8b and 9b with an excess of mCPBA through a five-step cascade process to yield the bicyclic lactone 27 as a potential precursor of racemic β-carbaxylose. Keywords: Captodative alkenes, 1-Acetylvinyl p-nitrobenzoyloxy, α-Keto carbinols, α-Ketol rearrangement, Cascade process, mCPBA |
| Databáze: | OpenAIRE |
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