Homogeneous, Supramolecular and Bio-Inspired Catalysis Van't Hoff Institute for Molecular Sciences, University of Amsterdam, Science Park 904, 1098 XH, Amsterdam, The Netherlands.
Chem Asian J. 2020 Mar 16;15(6):867-875. doi: 10.1002/asia.201901771. Epub 2020 Feb 21.
Supramolecular capsules can be used to change the activity and selectivity of a catalyst through the influence of the second coordination sphere, reminiscent of how enzymes control the selectivity of their processes. In enzymes, this approach is used to also control the enantioselectivity of reactions in which the active catalytic site is often not chiral but the second coordination sphere is. We are interested in the possibility to generate a chiral second coordination sphere around an otherwise achiral transition metal complex for asymmetric catalysis. In this paper we show that the ligand template approach can be used to generate a chiral second coordination sphere around a rhodium complex, which is used in asymmetric hydroformylation.
超分子胶囊可以通过第二配位球的影响来改变催化剂的活性和选择性,这让人想起了酶如何控制其反应的选择性。在酶中,这种方法也用于控制反应的对映选择性,其中活性催化位点通常是非手性的,但第二配位球是手性的。我们对在非手性过渡金属配合物周围产生手性第二配位球以进行不对称催化的可能性感兴趣。在本文中,我们表明配体模板法可用于在用于不对称氢甲酰化的铑配合物周围生成手性第二配位球。