Department of Organic Chemistry, Stockholm University, Svante Arrhenius väg 16C, SE-10691 Stockholm, Sweden.
School of Chemistry and Physics, University of Kwazulu-Natal, Private Bag X54001, Durban 4000, South Africa.
J Am Chem Soc. 2021 Dec 8;143(48):20377-20383. doi: 10.1021/jacs.1c09975. Epub 2021 Nov 22.
Homogeneous and heterogeneous catalyzed reactions can seldom operate synergistically under the same conditions. Here we communicate the use of a single rhodium precursor that acts in both the homogeneous and heterogeneous phases for the asymmetric full saturation of vinylarenes that, to date, constitute an unmet bottleneck in the field. A simple asymmetric hydrogenation of a styrenic olefin, enabled by a ligand accelerated effect, accounted for the facial selectivity in the consecutive arene hydrogenation. Tuning the ratio between the phosphine ligand and the rhodium precursor controlled the formation of homogeneous and heterogeneous catalytic species that operate without interference from each other. The system is flexible in terms of both the chiral ligand and the nature of the external olefin. We anticipate that our findings will promote the development of asymmetric arene hydrogenations.
均相和多相催化反应很少能在相同条件下协同进行。在这里，我们使用一种单一的铑前体，它在均相和多相两种相中都能发挥作用，用于不对称完全饱和乙烯基芳烃，这在迄今为止的领域中构成了一个未满足的瓶颈。通过配体加速效应实现的简单不对称氢化，解释了连续芳族氢化中面选择性。调节膦配体和铑前体之间的比例控制了均相和多相催化物种的形成，它们彼此之间没有干扰。该体系在手性配体和外部烯烃的性质方面都具有灵活性。我们预计我们的发现将促进不对称芳族氢化的发展。
