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Mechanistic and kinetic insights of reduction of indophenol by sodium borohydride: A theoretical study to explore the effect of solvent and counter ion
Chemical Physics ( IF 2.3 ) Pub Date : 2018-02-21 , DOI: 10.1016/j.chemphys.2018.02.021
Priyanka Patel , Sudheer Lingayat , Nitin Gulvi , Purav Badani

NaBH4 finds plethora of applications in organic synthesis due to its unique capability of chemo-selective reduction of carbonyl functional group. Present work is focussed to explore the energetically feasible reaction pathway for reduction of indophenol by sodium borohydride. Our calculations suggest following reaction steps for reduction of indophenol. The reduction reaction is initially driven via an asynchronous nucleophilic attack of borohydride ion on carbonyl group of indophenol. Intermediate generated is subjected to concurrent, hydroxyl ion assisted, proton abstraction followed by protonation of nucleophilic rich site on the molecule. Finally, reduction process undergoes completion by hydrolysis. Potential energy surface suggest that initial step of the reduction reaction is a rate determining step (RDS). More importantly, the synergistic effect of solvent and counter ion was observed to increase the electrophilicity of carbonyl carbon and thereby assisting in lowering energy barrier of RDS. This, in turn, enhances the reaction rate significantly.



中文翻译:

硼氢化钠还原吲哚酚的机理和动力学见解:探讨溶剂和抗衡离子作用的理论研究

碳酸氢钠4由于其化学选择性还原羰基官能团的独特能力,在有机合成中发现了许多应用。目前的工作集中在探索在能量上可行的硼氢化钠还原吲哚酚的反应途径。我们的计算表明,以下反应步骤可降低吲哚酚。还原反应最初是通过硼氢化物离子对吲哚酚的羰基的异步亲核攻击来驱动的。产生的中间体同时进行氢氧离子辅助的质子提取,然后对分子上亲核富集的位进行质子化。最后,还原过程通过水解完成。势能表面表明还原反应的初始步骤是速率确定步骤(RDS)。更重要的是,观察到溶剂和抗衡离子的协同作用增加了羰基碳的亲电性,从而有助于降低RDS的能垒。反过来,这显着提高了反应速率。

更新日期:2018-02-21
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