Supramolecular control of selectivity in transition-metal catalysis through substrate preorganization

Supramolecular chemistry exploits multiple weak intermolecular interactions to assemble nano-sized molecular architectures, providing new possibilities for (transition metal) catalyst development. In this Perspective we focus on the application of such weak (directional) interactions between a subst...

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Published in:Chemical science (Cambridge) Vol. 5; no. 6; pp. 2135 - 2145
Main Authors: Dydio, Pawe, Reek, Joost N. H
Format: Journal Article
Language:English
Published: 01-01-2014
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Summary:Supramolecular chemistry exploits multiple weak intermolecular interactions to assemble nano-sized molecular architectures, providing new possibilities for (transition metal) catalyst development. In this Perspective we focus on the application of such weak (directional) interactions between a substrate molecule and a (bifunctional) catalyst for structural preorganization prior to the catalytic reaction. As we discuss, such effects together with the confinement properties of the nano-space of the 'active sites' play a crucial role for the exceptional selectivities and activities of natural enzymes. We will elaborate on the application of such supramolecular strategy to the more traditional transition-metal catalysis, and we will compare it with the traditional substrate preorganization methods. Subsequently, literature examples of such bifunctional catalyst systems will be described in which the function of weak interactions was carefully designed a priori , as well as, the serendipitously found catalysts in which the presence of supramolecular effects was recognized post factum . The discussed examples demonstrate the power of the strategy for the control of selectivity in various types of metal catalyzed reactions, and the observation of the serendipitous findings can help to generate new leads for more efficient catalyst design. The Perspective highlights possibilities to use supramolecular interactions between a substrate molecule and a (bifunctional) catalyst as a powerful tool to control the selectivity in transition-metal catalysis.
Bibliography:Pawe Dydio (1985) studied Natural Sciences and Mathematics at the University of Warsaw, Poland (2004-2009), graduating in Chemistry (summa cum laude). While at UW, he did undergraduate research in supramolecular chemistry with Professor Janusz Jurczak. Subsequently, he joined the group of Professor Joost Reek at the University of Amsterdam, the Netherlands, and working on the discovery and development of supramolecular strategies in homogeneous transition-metal catalysis he completed his PhD (cum laude) in 2013. He is currently a postdoctoral researcher in the group of Professor John Hartwig at the University of California Berkeley, USA.
Joost Reek (1967) completed his PhD in Nijmegen in 1996 in the area of supramolecular chemistry with Prof. Nolte. After a postdoctoral fellowship in Sydney, Australia, with Prof. M. Crossley, he joined the group of Prof. van Leeuwen at the University of Amsterdam as an assistant professor in 1998, with his research activities focusing on transition-metal catalysis. In 2005 he was elected to become a member of The Young Academy of Science (KNAW). In 2006 he became full professor (chair in supramolecular catalysis). He has received various prestigious grants, including VICI (2006) and an ERC advanced grant (2013). In 2009 he also started a spin-off company, InCatT, to explore the commercial potential of new supramolecular strategies for combinatorial approaches to find catalysts for (asymmetric) chemical transformations. In 2013 he became an elected member of Royal Holland Society of Sciences and Humanities (KHMW), and scientific director of the van 't Hoff institute for molecular sciences. His current research activities include transition-metal catalysis, supramolecular catalysis and catalysis for green energy applications.
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ISSN:2041-6520
2041-6539
DOI:10.1039/c3sc53505c