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Rh(i)-catalyzed dimerization of ene-vinylidenecyclopropanes for the construction of spiro[4,5]decanes and mechanistic studies
Rh(i) complex catalyzed dimerization of ene-vinylidenecyclopropanes took place smoothly to construct a series of products containing spiro[4,5]decane skeletons featuring a simple operation procedure, mild reaction conditions, and good functional group tolerance. In this paper, the combination of exp...
| Autores principales: | , , , |
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| Formato: | Online Artículo Texto |
| Lenguaje: | English |
| Publicado: |
The Royal Society of Chemistry
2022
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| Materias: | |
| Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9214856/ https://www.ncbi.nlm.nih.gov/pubmed/35799819 http://dx.doi.org/10.1039/d1sc06986a |
| Sumario: | Rh(i) complex catalyzed dimerization of ene-vinylidenecyclopropanes took place smoothly to construct a series of products containing spiro[4,5]decane skeletons featuring a simple operation procedure, mild reaction conditions, and good functional group tolerance. In this paper, the combination of experimental and computational studies reveals a counterion-assisted Rh(i)–Rh(iii)–Rh(v)–Rh(iii)–Rh(i) catalytic cycle involving tandem oxidative cyclometallation/reductive elimination/selective oxidative addition/selective reductive elimination/reductive elimination steps; in addition, a pentavalent spiro-rhodium intermediate is identified as the key intermediate in this dimerization reaction upon DFT calculation. |
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