Mechanism of alkoxy groups substitution by Grignard reagents on aromatic rings and experimental verification of theoretical predictions of anomalous reactions.
Mechanism of alkoxy groups substitution by Grignard reagents on aromatic rings and experimental verification of theoretical predictions of anomalous reactions.
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DOI：
10.1021/ja4015937
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发表时间：
2013-05-01
影响因子：
15
通讯作者：
Houk, K. N.
中科院分区：
文献类型：
--
作者：
Jimenez-Oses, Gonzalo;Brockway, Anthony J.;Shaw, Jared T.;Houk, K. N.
用格氏试剂直接置换葡萄酸酯和芳香酯中的烷氧基的机理，计算地阐明了这一反应，这一反应与预期中较好的苯氧基离去基没有关系。该反应的机理已确定为镁的亲核烷基通过甲氧烷过渡态向反应碳的球内攻击。与反应的烷氧基和羰基形成强镁螯合物决定了观察到的反应活性和选择性。考察了酯、酮、醛取代基对反应的影响。在某些情况下，计算预测的产物形成与先前报道的不同；这些预测随后被实验证实。研究实际系统的重要性，而不是简化模型作为计算系统，被证明。
The mechanism of direct displacement of alkoxy groups in vinylogous and aromatic esters by Grignard reagents, a reaction that is not observed with expectedly better tosyloxy leaving groups, is elucidated computationally. The mechanism of this reaction has been determined to proceed through the inner-sphere attack of nucleophilic alkyl groups from magnesium to the reacting carbons via a metalaoxetane transition state. The formation of a strong magnesium chelate with the reacting alkoxy and carbonyl groups dictates the observed reactivity and selectivity. The influence of ester, ketone and aldehyde substituents was investigated. In some cases, the calculations predicted the formation of products different than those previously reported; these predictions were then verified experimentally. The importance of studying the actual system, and not simplified models as computational systems, is demonstrated.
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DOI：
10.1039/p19840001043
发表时间：
1984-01-01
期刊：
JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 1
影响因子：
--
作者：
CARPENTER, TA;EVANS, GE;WILKINSON, MR
通讯作者：
WILKINSON, MR
影响因子：
--
作者：
GONZALEZ, C;SCHLEGEL, HB
通讯作者：
SCHLEGEL, HB
影响因子：
2.8
作者：
BAUSCHLICHER, CW
通讯作者：
BAUSCHLICHER, CW
影响因子：
15
作者：
FUSON, RC;WASSMUNDT, FW
通讯作者：
WASSMUNDT, FW
影响因子：
4.4
作者：
BECKE, AD
通讯作者：
BECKE, AD