Homogeneous, Supramolecular and Bio-Inspired Catalysis, Van't Hoff Institute for Molecular Sciences, University of Amsterdam, Science Park 904, 1098 XH, Amsterdam, The Netherlands.
Radboud University, Institute for Molecules and Materials, Heyendaalseweg 135, 6525 AJ, Nijmegen, The Netherlands.
Angew Chem Int Ed Engl. 2019 Feb 25;58(9):2696-2699. doi: 10.1002/anie.201812610. Epub 2019 Jan 29.
Supramolecular approaches in transition-metal catalysis, including catalyst encapsulation, have attracted considerable attention. Compared to enzymes, supramolecular catalysts in general are less complex. Enzyme activity is often controlled by the use of smaller cofactor molecules, which is important in order to control reactivity in complex mixtures of molecules. Interested in increasing complexity and allowing control over supramolecular catalyst formation in response to external stimuli, we designed a catalytic system that only forms an efficient supramolecular complex when a small cofactor molecule is added to the solution. This in turn affects both the activity and selectivity when applied in a hydroformylation reaction. This contribution shows that catalyst encapsulation can be controlled by the addition of a cofactor, which affects crucial catalyst properties.
超分子方法在过渡金属催化中,包括催化剂封装,已经引起了相当大的关注。与酶相比,超分子催化剂通常较为简单。酶活性通常通过使用较小的辅助因子分子来控制,这对于控制复杂分子混合物中的反应性非常重要。我们有兴趣增加复杂性,并允许对外界刺激做出响应来控制超分子催化剂的形成,因此设计了一种催化体系,只有当向溶液中添加小分子辅助因子时,才会形成有效的超分子复合物。这反过来又会影响在氢甲酰化反应中的活性和选择性。本研究表明,催化剂封装可以通过添加辅助因子来控制,这会影响关键的催化剂性质。