Synthesis and Reactivity of Dibenzoselenacycloheptynes
Synthesis and Reactivity of Dibenzoselenacycloheptynes
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DOI：
10.1021/ol401225n
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发表时间：
2013-06-21
期刊：
影响因子：
5.2
通讯作者：
Bertozzi, Carolyn R.
中科院分区：
文献类型：
--
作者：
de Almeida, Gabriela;Townsend, Lisa C.;Bertozzi, Carolyn R.
二苯并硒环庚炔由市售试剂分三步制备，并用苄基叠氮化物原位捕获以形成相应的三唑。令人惊讶的是，二苯并硒环庚炔还从溶剂如THF或甲苯中夺取氢原子，形成二苯并硒环庚烯产物。这些烯基化合物是由从溶剂到不可溶中间体的氢转移反应产生的，我们假设该反应通过源自具有异常高自由基特征的紧张炔基键的自由基机制进行。
Dibenzoselenacycloheptynes were prepared in three steps from commercially available reagents and trapped in situ with benzyl azide to form the corresponding triazoles. Surprisingly, the dibenzoselenacycloheptynes also abstracted hydrogen atoms from solvents such as THF or toluene, forming dibenzoselenacycloheptene products. These alkenyl compounds arise from a hydrogen transfer reaction from solvent to the unisolable Intermediate, and we postulate that the reaction proceeds via a radical mechanism originating from the strained alkynyl bond that has unusually high radical character.