Photochemical generation and trapping of 3-oxacyclohexyne
Photochemical generation and trapping of 3-oxacyclohexyne
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DOI：
10.1039/c7ob01697b
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发表时间：
2017-10-21
影响因子：
3.2
通讯作者：
Thamattoor, Dasan M.
中科院分区：
文献类型：
--
作者：
Fan, Rui;Wen, Yuewei;Thamattoor, Dasan M.
以环丙化菲为前驱体，首次光化学合成了3-氧环己炔，并以Diels-Alder加合物的形式被环戊二烯捕获。该前体最初产生假定的3-氧环戊二烯，随后重排为环炔。计算研究表明，碳烯倾向于单重态，近端碳向氧的1,2位移对其环膨胀的势垒能量低于远端碳的相应位移。
The strained heterocyclic alkyne, 3-oxacyclohexyne, was generated photochemically for the first time using a cyclopropanated phenanthrene precursor, and trapped by cyclopentadienones as Diels-Alder adducts. The precursor initially produced the putative 3-oxacyclopentylidenecarbene that subsequently rearranged to the cycloalkyne. Computational studies indicate that the carbene favors a singlet state, and the barrier for its ring expansion by a 1,2-shift of the carbon proximal to oxygen is lower in energy than the corresponding shift of the distal carbon.