Samarium(III) carbenoid as a competing reactive species in samarium-promoted cyclopropanation reactions.
Samarium(III) carbenoid as a competing reactive species in samarium-promoted cyclopropanation reactions.
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钐(III)类胡萝卜素作为钐促进的环丙烷化反应中的竞争活性物质。
DOI：
10.1021/jo0494679
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发表时间：
2004
期刊：
影响因子：
--
通讯作者：
D. Phillips
中科院分区：
文献类型：
--
作者：
Dongqi Wang;Cunyuan Zhao;D. Phillips
三价钐类卡宾I2 SmCH 2 I促进与乙烯的环丙烷化反应进行了研究，并预测是高度反应性的，类似于二价钐类卡宾ISmCH 2 I。探讨了亚甲基转移和碳酰化途径，并比较了THF溶剂分子与类卡宾的配位情况。发现亚甲基转移是有利的，反应的势垒从12.9到9.2千卡/摩尔，相比之下，在加入一个THF分子后，碳化途径的势垒为15.4-17.5千卡/摩尔。
The trivalent samarium carbenoid I2SmCH2I-promoted cyclopropanation reactions with ethylene have been investigated and are predicted to be highly reactive, similarly to the divalent samarium carbenoid ISmCH2I. The methylene transfer and carbometalation pathways were explored and compared with and without coordination of THF solvent molecules to the carbenoid. The methylene transfer was found to be favored, with the barrier to reaction going from 12.9 to 9.2 kcal/mol compared to barriers of 15.4-17.5 kcal/mol for the carbometalation pathway upon the addition of one THF molecule.