Bian, H.-D.; Huang, F.-P.

RSC Adv. 2016, 6, 44154-44162, 10.1039/C6RA08153C

Enantioselective oxidation of a series of alkyl aryl sulfides catalyzed by a novel VIV8 cluster is tested in an aqueous medium in the presence of serum albumin. The procedure is simple, environmentally friendly, selective, and highly reactive.

Liu, X.; Wang, J.; Wu, Y.; Zhong, F.

J. Am. Chem. Soc. 2021, 143, 617-622, 10.1021/jacs.0c10882

Devising artificial photoenzymes for abiological bond-forming reactions is of high synthetic value but also a tremendous challenge. Disclosed herein is the first photobiocatalytic cross-coupling of aryl halides enabled by a designer artificial dehalogenase, which features a genetically encoded benzophenone chromophore and site-specifically modified synthetic NiII(bpy) cofactor with tunable proximity to streamline the dual catalysis. Transient absorption studies suggest the likelihood of energy transfer activation in the elementary organometallic event. This design strategy is viable to significantly expand the catalytic repertoire of artificial photoenzymes for useful organic transformations.

Bian, H.-D.; Liang, H.

Dalton Trans. 2016, 45, 8061-8072, 10.1039/C5DT04507J

An artificial metalloenzyme (BSA–CoL) based on the incorporation of a cobalt(ii) Schiff base complex {CoL, H2L = 2,2′-[(1,2-ethanediyl)bis(nitrilopropylidyne)]bisphenol} with bovine serum albumin (BSA) has been synthesized and characterized.

Luk, L.Y.P.

RSC Adv. 2020, 10, 16147-16161, 10.1039/d0ra01526a

In this review, the development of organocatalytic artificial enzymes will be discussed. This area of protein engineering research has underlying importance, as it enhances the biocompatibility of organocatalysis for applications in chemical and synthetic biology research whilst expanding the catalytic repertoire of enzymes. The approaches towards the preparation of organocatalytic artificial enzymes, techniques used to improve their performance (selectivity and reactivity) as well as examples of their applications are presented. Challenges and opportunities are also discussed.

Bian, H.-D.; Huang, F.-P.

Tetrahedron: Asymmetry 2017, 28, 1700-1707, 10.1016/j.tetasy.2017.10.021

Four coordination complexes ML derived from an achiral Schiff base ligand (H2L = 2,2′-[(1,2-ethanediyl)bis(nitrilopropylidyne)]bisphenol) have been synthesized and characterized. A method is described for the enantioselective oxidation of a series of aryl alkyl sulfides using the coordination complexes in the presence of serum albumins (SAs) in an aqueous medium at ambient temperature. The mixture of metal complexes with serum albumins is useful for inducing asymmetric catalysis. The complex, albumin source and substrate influence stereoselective sulfoxidation. At optimal pH with the appropriate oxidant, some of ML/SA systems are identified as very efficient catalysts, giving the corresponding sulfoxides in excellent chemical yield (up to 100%) and good enantioselectivity (up to 94% ee) in certain cases. UV–visible spectroscopic data provide evidence that stronger binding between the complex and serum albumin lead to higher enantioselectivity.

Luk, L.Y.P.

Chem. Commun. 2021, 57, 1919-1922, 10.1039/d0cc08142f

Here, the streptavidin–biotin technology was applied to enable organocatalytic transfer hydrogenation. By introducing a biotin-tethered pyrrolidine (1) to the tetrameric streptavidin (T-Sav), the resulting hybrid catalyst was able to mediate hydride transfer from dihydro-benzylnicotinamide (BNAH) to α,β-unsaturated aldehydes. Hydrogenation of cinnamaldehyde and some of its aryl-substituted analogues was found to be nearly quantitative. Kinetic measurements revealed that the T-Sav:1 assembly possesses enzyme-like behavior, whereas isotope effect analysis, performed by QM/MM simulations, illustrated that the step of hydride transfer is at least partially rate-limiting. These results have proven the concept that T-Sav can be used to host secondary amine-catalyzed transfer hydrogenations.