Combining enzymes and organometallic complexes: novel artificial metalloenzymes and hybrid systems for C–H activation chemistry

Abstract

This review describes the advances in the design and application of novel artificial metalloenzymes in C–H activation reactions.

Enantioselective Hydroxylation of Benzylic C(sp3)–H Bonds by an Artificial Iron Hydroxylase Based on the Biotin–Streptavidin Technology

“…To complement homogeneous catalysts and enzymes, artificial metalloenzymes (ArMs), that result from anchoring an abiotic cofactor within a macromolecular scaffold, have attracted increasing interest in the past years. The well-defined secondary coordination sphere around the cofactor provided by the protein offers fascinating perspectives to optimize both activity and selectivity of the ArMs. − In this context several protein scaffolds have proven versatile . These include carbonic anhydrase, hemoproteins, , proline oligopeptidase, lactococcal multiresistance regulator, four helix bundles, , nitrobindin, (strept)­avidin, − etc.…”

An Introductory Overview of C–H Bond Activation/ Functionalization Chemistry with Focus on Catalytic C(sp3)–H Bond Borylation

“…For example, inputs from theoretical and information scientists greatly help experimental scientists in their quest for efficient catalyst design. Advances in modern biological sciences have also prompted the creation of synthetic biomimetic systems that functionally perform chemical reactivities exhibited by natural enzymes (Chen and Arnold, 2020;Thompson and Cowan, 2020;Perez-Rizquez et al, 2019;Reyes and Tanaka, 2017). Only now that we begin to have a complete understanding that even synthetic catalysts in most parts mimic the mechanistic attributes of natural enzymes including the involvement of non-covalent interactions (Fanourakis et al, 2020) to stabilize the transition states associated with C-H bond functionalization within a generated catalytic pocket.…”

The various levels of integration of chemo- and bio-catalysis towards hybrid catalysis

“…This gave rise to the development of innovative systems bridging the two disciplines by incorporating chemical catalysts directly into biological structures, such as catalytic peptides and artificial enzymes. 34,[61][62][63][64][65][66][67][68] Despite this strong source of inspiration, there remain far fewer examples of multicatalytic reactions in chemical catalysis than in biocatalysis. This is even more evident for 1P1S reactions.…”