Exploring diradical chemistry: a carbon-centered radical may act as either an anion or electrophile through an orbital isomer.
Exploring diradical chemistry: a carbon-centered radical may act as either an anion or electrophile through an orbital isomer.
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DOI：
10.1002/anie.201411334
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发表时间：
2015-04
影响因子：
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通讯作者：
Théo P. Gonçalves;Mubina Mohamed;R. Whitby;H. Sneddon;D. Harrowven
中科院分区：
文献类型：
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作者：
Théo P. Gonçalves;Mubina Mohamed;R. Whitby;H. Sneddon;D. Harrowven
由炔基环丁烯酮热裂解形成的双自由基中间体，由于具有两性离子和环己烯酮特征的轨道异构体的存在，可以表现出自由基、阴离子或亲电性。我们认识到水、醇和某些取代基可以诱导这种转换，这为合成提供了新的机会。例如，它可以用来关闭自由基途径，并使羰基碳酸酯和四取代醌接近。
Diradical intermediates, formed by thermolysis of alkynylcyclobutenones, can display radical, anion, or electrophilic character because of the existence of an orbital isomer with zwitterionic and cyclohexatrienone character. Our realization that water, alcohols, and certain substituents can induce the switch provides new opportunities in synthesis. For example, it can be used to shut down radical pathways and to give access to aryl carbonates and tetrasubstituted quinones.