Intermolecular reductive radical addition to 2-(2,2,2-trifluoroethylidene)-1,3-dithiane 1-oxide: experimental and theoretical studies.
Intermolecular reductive radical addition to 2-(2,2,2-trifluoroethylidene)-1,3-dithiane 1-oxide: experimental and theoretical studies.
复制标题
2-(2,2,2-三氟亚乙基)-1,3-二噻烷 1-氧化物的分子间还原自由基加成：实验和理论研究。
DOI：
10.1021/ol1025926
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发表时间：
2010
期刊：
影响因子：
5.2
通讯作者：
K. Oshima
中科院分区：
文献类型：
--
作者：
Ryota Nakayama;H. Matsubara;Daishi Fujino;Takayuki Kobatake;S. Yoshida;H. Yorimitsu;K. Oshima
设计了氢化锡介导的有机卤化物与2-(2,2,2-三氟亚乙基)-1,3-二噻烷1-氧化物的自由基加成。该反应相当于三氟甲基乙烯酮上不可实现的自由基加成，提供有用的α-三氟甲基羰基等价物。底物的三氟甲基和亚砜基团对于自由基加成的成功、降低自由基加成步骤的势垒并控制反应的立体选择性起着关键作用，DFT 计算已经阐明了这一点。
Tin hydride mediated radical addition of organic halide to 2-(2,2,2-trifluoroethylidene)-1,3-dithiane 1-oxide has been devised. The reaction is equivalent to an unrealizable radical addition to trifluoromethylketene, providing useful α-trifluoromethyl carbonyl equivalents. The trifluoromethyl and the sulfoxide groups of the substrate play key roles for the success of the radical addition, lowering the barrier of the radical addition step and controlling the stereoselectivity of the reaction, which DFT calculations have elucidated.