Computational studies on a carbenoid mechanism for the Doering-Moore-Skattebøl reaction.
Computational studies on a carbenoid mechanism for the Doering-Moore-Skattebøl reaction.
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Doering-Moore-Skattebøl 反应的类胡萝卜素机理的计算研究。
DOI：
10.1021/jo401847v
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发表时间：
2013
期刊：
影响因子：
--
通讯作者：
Richard P. Johnson
中科院分区：
文献类型：
--
作者：
Alicia C. Voukides;Katharine J. Cahill;Richard P. Johnson
双卤环丙烷与金属或烷基锂反应生成卡宾，这些卡宾在低温下对烯烃开环，这就是众所周知的多林-摩尔-斯凯特博-L反应。用密度泛函理论和CCSD(T)//密度泛函方法模拟了1-溴-1-锂硫代环丙烷的结构、配位状态和开环情况，作为环丙卡宾化学的模型。采用了隐式(PCM)和显式溶剂化模型。类卡宾开环的过程类似于早期对环丙叉的研究中预测的过程。最初的不旋转立体化学在通往联烯-溴化锂络合物的过程中变成了旋转的。计算不支持将类卡宾预解离为环丙叉+溴化锂。密度泛函计算预测，无论有无溶剂化，类卡宾都会适度地发生电子二聚反应，二聚体似乎是溶液中最有可能的反应物种。预测的开环势垒只受到溶剂化或二聚体形成的轻微影响，始终保持在9-12千卡/摩尔的范围内。
The reaction of geminal dihalocyclopropanes with metals or alkyllithiums affords carbenoids which undergo low-temperature ring opening to allenes; this is known as the Doering-Moore-Skattebøl reaction. DFT and CCSD(T)//DFT computations have been used to model the structure, coordination state, and ring opening of 1-bromo-1-lithiocyclopropane as a model for cyclopropylcarbenoid chemistry. Both implicit (PCM) and explicit solvation models have been applied. Carbenoid ring opening is similar to the process predicted in earlier studies on cyclopropylidene. The initial disrotatory stereochemistry becomes conrotatory en route to the allene-LiBr complex. Predissociation of the carbenoid to cyclopropylidene + LiBr is not supported by computations. DFT computations predict modestly exergonic dimerization of the carbenoid, with or without solvation, and the dimer appears to be the most likely reactive species in solution. Predicted barriers to ring opening are only modestly affected by solvation or by dimer formation, remaining in the range of 9-12 kcal/mol throughout.
影响因子：
3.3
作者：
Rehbein, Julia;Carpenter, Barry K.
通讯作者：
Carpenter, Barry K.