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Mechanistic Investigation into the Acetate-Initiated Catalytic Trimerization of Aliphatic Isocyanates: A Bicyclic Ride.
The Journal of Organic Chemistry ( IF 3.3 ) Pub Date : 2020-06-08 , DOI: 10.1021/acs.joc.0c00944 Max Siebert 1 , Rebecca Sure 2 , Peter Deglmann 2 , Anna C Closs 1 , Frederic Lucas 2 , Oliver Trapp 1
The Journal of Organic Chemistry ( IF 3.3 ) Pub Date : 2020-06-08 , DOI: 10.1021/acs.joc.0c00944 Max Siebert 1 , Rebecca Sure 2 , Peter Deglmann 2 , Anna C Closs 1 , Frederic Lucas 2 , Oliver Trapp 1
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The acetate-initiated aliphatic isocyanate trimerization to isocyanurate was investigated by state-of-the-art analytical and computational methods. Although the common cyclotrimerization mechanism assumes the consecutive addition of three equivalents of isocyanate to acetate prior to product formation, we found that the underlying mechanism is more complex. In this work, we demonstrate that the product, in fact, is formed via the connection of two unexpected catalytic cycles, with acetate being only the precatalyst. The initial discovery of a precatalyst activation by quantum chemical computations and the resulting first catalysis cycle were corroborated by mass spectrometric and NMR experiments, thereby additionally revealing a catalyst migration to the second catalytic cycle. These results were further confirmed by computations, completing the full mechanistic understanding of this catalytic system. Identification of a side product with undesired properties for final coating applications allows for process optimization in the chemical industry.
中文翻译：
乙酸酯引发的脂肪族异氰酸酯催化三聚的机理研究：双环化合物。
通过最新的分析和计算方法研究了乙酸酯引发的脂族异氰酸酯三聚为异氰脲酸酯。尽管常见的环三聚化机理假定在产物形成之前将三当量的异氰酸酯连续添加到乙酸盐中，但我们发现基本机理更为复杂。在这项工作中，我们证明了该产品实际上是通过两个意外的催化循环的连接而形成的，其中乙酸盐只是前催化剂。质谱和NMR实验证实了通过量子化学计算对前催化剂活化的最初发现以及由此产生的第一催化循环，从而进一步揭示了催化剂向第二催化循环的迁移。计算结果进一步证实了这些结果，完成对该催化系统的全面机械理解。鉴定最终涂层应用中具有不良性能的副产品可以优化化学工业中的工艺。
更新日期：2020-07-02
中文翻译：
乙酸酯引发的脂肪族异氰酸酯催化三聚的机理研究：双环化合物。
通过最新的分析和计算方法研究了乙酸酯引发的脂族异氰酸酯三聚为异氰脲酸酯。尽管常见的环三聚化机理假定在产物形成之前将三当量的异氰酸酯连续添加到乙酸盐中，但我们发现基本机理更为复杂。在这项工作中，我们证明了该产品实际上是通过两个意外的催化循环的连接而形成的，其中乙酸盐只是前催化剂。质谱和NMR实验证实了通过量子化学计算对前催化剂活化的最初发现以及由此产生的第一催化循环，从而进一步揭示了催化剂向第二催化循环的迁移。计算结果进一步证实了这些结果，完成对该催化系统的全面机械理解。鉴定最终涂层应用中具有不良性能的副产品可以优化化学工业中的工艺。
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