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有机催化过程中表观负活化焓的动力学证据。

Kinetic evidence of an apparent negative activation enthalpy in an organocatalytic process.

机构信息

KAUST Catalysis Center and Division of Physical Science and Engineering, King Abdullah University of Science and Technology, Thuwal, Kingdom of Saudi Arabia.

出版信息

Sci Rep. 2013;3:2557. doi: 10.1038/srep02557.

DOI:10.1038/srep02557
PMID:23990028
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC3757351/
Abstract

A combined kinetic and computational study on our tryptophan-based bifunctional thiourea catalyzed asymmetric Mannich reactions reveals an apparent negative activation enthalpy. The formation of the pre-transition state complex has been unambiguously confirmed and these observations provide an experimental support for the formation of multiple hydrogen bonding network between the substrates and the catalyst. Such interactions allow the creation of a binding cavity, a key factor to install high enantioselectivity.

摘要

对基于色氨酸的双功能硫脲催化的不对称曼尼希反应的动力学和计算研究表明，该反应具有明显的负活化焓。前过渡态复合物的形成已被明确证实，这些观察结果为底物与催化剂之间形成多个氢键网络提供了实验支持。这种相互作用允许形成一个结合腔，这是实现高对映选择性的关键因素。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8b96/3757351/2b496f7f1b6c/srep02557-f5.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8b96/3757351/fe2e565f8642/srep02557-f1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8b96/3757351/31089f163771/srep02557-f2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8b96/3757351/82810acfc33b/srep02557-f3.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8b96/3757351/5c40b1f3326b/srep02557-f4.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8b96/3757351/2b496f7f1b6c/srep02557-f5.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8b96/3757351/fe2e565f8642/srep02557-f1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8b96/3757351/31089f163771/srep02557-f2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8b96/3757351/82810acfc33b/srep02557-f3.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8b96/3757351/5c40b1f3326b/srep02557-f4.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8b96/3757351/2b496f7f1b6c/srep02557-f5.jpg

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