A supramolecular microenvironment strategy for transition metal catalysis
A supramolecular microenvironment strategy for transition metal catalysis
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DOI：
10.1126/science.aad3087
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发表时间：
2015-12-04
期刊：
影响因子：
56.9
通讯作者：
Toste, F. Dean
中科院分区：
文献类型：
--
作者：
Kaphan, David M.;Levin, Mark D.;Toste, F. Dean
据报道，自组装超分子络合物催化高价过渡金属络合物[如金（III）和铂（IV）]的烷基-烷基还原消除，这是许多催化过程中的中心键形成基本步骤。超分子组装的催化微环境充当功能性酶模拟物，将酶催化的概念应用于生物学中不存在的反应性歧管。动力学实验描述了一种米氏型机制，测量的速率加速度（k（cat）/k（uncat））高达1.9 × 10（7）（此处k（cat）和k（uncat）分别为米氏酶促速率常数和观察到的非催化速率常数）。这种模式已被进一步纳入到一个双重催化交叉偶联反应，这需要超分子微环境催化剂和过渡金属催化剂协同工作，以实现有效的营业额。
A self-assembled supramolecular complex is reported to catalyze alkyl-alkyl reductive elimination from high-valent transition metal complexes [such as gold(III) and platinum(IV)], the central bond-forming elementary step in many catalytic processes. The catalytic microenvironment of the supramolecular assembly acts as a functional enzyme mimic, applying the concepts of enzymatic catalysis to a reactivity manifold not represented in biology. Kinetic experiments delineate a Michaelis-Menten-type mechanism, with measured rate accelerations (k(cat)/k(uncat)) upto 1.9x10(7) (here k(cat) and k(uncat) are the Michaelis-Menten enzymatic rate constant and observed uncatalyzed rate constant, respectively). This modality has further been incorporated into a dual catalytic cross-coupling reaction, which requires both the supramolecular microenvironment catalyst and the transition metal catalyst operating in concert to achieve efficient turnover.