Thiophosphonium–Alkyne Cycloaddition Reactions: A Heavy Congener of the Carbonyl–Alkyne Metathesis
| Autor: | Milica Feldt, Pawel Löwe, Lukas F. B. Wilm, Fabian Dielmann, Maike B. Röthel |
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| Rok vydání: | 2021 |
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| Zdroj: | Inorganic Chemistry |
| ISSN: | 1520-510X 0020-1669 |
| DOI: | 10.1021/acs.inorgchem.1c02076 |
| Popis: | While the metathesis reaction between alkynes and thiocarbonyl compounds has been thoroughly studied, the reactivity of alkynes with isoelectronic main group R2E=S compounds is rarely reported and unknown for [R2P=S]+ analogues. We show that thiophosphonium ions, which are the isoelectronic phosphorus congeners to thiocarbonyl compounds, undergo [2 + 2]-cycloaddition reactions with different alkynes to generate 1,2-thiaphosphete ions. The four-membered ring species are in an equilibrium state with the corresponding P=C–C=S heterodiene structure and thus undergo hetero-Diels–Alder reactions with acetonitrile. Heteroatom and substituent effects on the energy profile of the 1,2-thiaphosphete formation were elucidated by means of quantum chemical methods. We show that thiophosphonium ions, which are the isoelectronic phosphorus congeners to thiocarbonyl compounds, undergo [2 + 2]-cycloaddition reactions with different alkynes to generate 1,2-thiaphosphete ions. The four-membered ring species are in an equilibrium state with the corresponding P=C−C=S heterodiene structure and thus undergo hetero-Diels−Alder reactions with acetonitrile. Heteroatom and substituent effects on the energy profile of the 1,2-thiaphosphete formation were elucidated by means of quantum chemical methods. |
| Databáze: | OpenAIRE |
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