Combining nanotechnology with the other science disciplines is necessary to produce various materials with nanoscale structural and functional information, which is nanoarchitectonics as a novel paradigm to create useful materials. One of the basic ideas in the nanoarchitectonics concept is use of molecular-level information to architect functional materials. This kind of strategy is indeed used in some pre-existing science fields and technical methods. For example, molecular imprinting technique provides functional materials possessing molecular information in insides of fabricated materials. Revisiting such known concept with the nanoarchitectonics concept would have great meaning in unification of individual research disciplines into one key concept. In this review, we survey fundamentals and recent trends of the molecular imprinting approaches upon consideration with the nanoarchitectonics. Here, aspects and examples of molecular imprinting are surveyed from fundamentals to advanced applications: (i) ...

Molecular Imprinting: Materials Nanoarchitectonics with Molecular Information

Light has received increased attention for various chemical reactions but also in combination with biocatalytic reactions. Because currently only a few enzymatic reactions are known, which per se require light, most transformations involving light and a biocatalyst exploit light either for providing the cosubstrate or cofactor in an appropriate redox state for the biotransformation. In selected cases, a promiscuous activity of known enzymes in the presence of light could be induced. In other approaches, light-induced chemical reactions have been combined with a biocatalytic step, or light-induced biocatalytic reactions were combined with chemical reactions in a linear cascade. Finally, enzymes with a light switchable moiety have been investigated to turn off/on or tune the actual reaction. This Review gives an overview of the various approaches for using light in biocatalysis.

Photo-Biocatalysis: Biotransformations in the Presence of Light

The Petasis boron–Mannich reaction, simply referred to as the Petasis reaction, is a powerful multicomponent coupling reaction of a boronic acid, an amine, and a carbonyl derivative. Highly functio...

Reactivity and Synthetic Applications of Multicomponent Petasis Reactions

Conjugated poly-ynes and poly(metalla-ynes) constitute an important class of new materials with potential application in various domains of science. The key factors responsible for the diverse usage of these materials is their intriguing and tunable chemical and photophysical properties. This review highlights fascinating advances made in the field of conjugated organic poly-ynes and poly(metalla-ynes) incorporating group 4–11 metals. This includes several important aspects of conjugated poly-ynes viz. synthetic protocols, bonding, electronic structure, nature of luminescence, structure–property relationships, diverse applications, and concluding remarks. Furthermore, we delineated the future directions and challenges in this particular area of research.

Rise of Conjugated Poly-ynes and Poly(Metalla-ynes): From Design Through Synthesis to Structure–Property Relationships and Applications

Electrochemistry grants direct access to reactive intermediates (radicals and ions) in a controlled fashion toward selective organic transformations. This feature has been demonstrated in a variety of alkene functionalization reactions, most of which proceed via an anodic oxidation pathway. In this report, we further expand the scope of electrochemistry to the reductive functionalization of alkenes. In particular, the strategic choice of reagents and reaction conditions enabled a radical-polar crossover pathway wherein two distinct electrophiles can be added across an alkene in a highly chemo- and regioselective fashion. Specifically, we used this strategy in the intermolecular carboformylation, anti-Markovnikov hydroalkylation, and carbocarboxylation of alkenes-reactions with rare precedents in the literature-by means of the electroreductive generation of alkyl radical and carbanion intermediates. These reactions employ readily available starting materials (alkyl halides, alkenes, etc.) and simple, transition-metal-free conditions and display broad substrate scope and good tolerance of functional groups. A uniform protocol can be used to achieve all three transformations by simply altering the reaction medium. This development provides a new avenue for constructing Csp3-Csp3 bonds.

Electroreductive Carbofunctionalization of Alkenes with Alkyl Bromides via a Radical-Polar Crossover Mechanism.

Propargylamines are a versatile class of compounds which find broad application in many fields of chemistry. This review aims to describe the different strategies developed so far for the synthesis of propargylamines and their derivatives as well as to highlight their reactivity and use as building blocks in the synthesis of chemically relevant organic compounds. In the first part of the review, the different synthetic approaches to synthesize propargylamines, such as A3 couplings and C–H functionalization of alkynes, have been described and organized on the basis of the catalysts employed in the syntheses. Both racemic and enantioselective approaches have been reported. In the second part, an overview of the transformations of propargylamines into heterocyclic compounds such as pyrroles, pyridines, thiazoles, and oxazoles, as well as other relevant organic derivatives, is presented.

/pdf/synthesis-and-reactivity-of-propargylamines-in-organic-2p342bmyhh.pdf

Synthesis and Reactivity of Propargylamines in Organic Chemistry

The synthesis of enantiomerically pure 1,3-mercaptoalkanol volatile sulfur compounds through a one-pot photo-biocatalytic cascade reaction is described. Two new KRED biocatalysts with opposite enantioselectivity were discovered and proved to be efficient on a wide range of substrates. The one-pot cascade reaction combining photocatalytic thio-Michael addition with biocatalytic ketoreduction in an aqueous medium provides a green and sustainable approach to enantiomerically pure 1,3-mercaptoalkanols in high yields with excellent enantioselectivity.

/pdf/photo-biocatalytic-one-pot-cascades-for-the-enantioselective-2ty2wrth06.pdf

Photo-biocatalytic One-Pot Cascades for the Enantioselective Synthesis of 1,3-Mercaptoalkanol Volatile Sulfur Compounds

The recent outbreaks of Zika virus (ZIKV) infection worldwide make the discovery of novel antivirals against flaviviruses a research priority. This work describes the identification of novel inhibitors of ZIKV through a structure-based virtual screening approach using the ZIKV NS5-MTase. A novel series of molecules with a carbazoyl-aryl-urea structure has been discovered and a library of analogues has been synthesized. The new compounds inhibit ZIKV MTase with IC50 between 23-48 μM. In addition, carbazoyl-aryl-ureas also proved to inhibit ZIKV replication activity at micromolar concentration.

https://chemistry-europe.onlinelibrary.wiley.com/doi/pdf/10.1002/cmdc.201900533

Design, Synthesis and Discovery of N,N'-Carbazoyl-aryl-urea Inhibitors of Zika NS5 Methyltransferase and Virus Replication.

The enantioselective synthesis of α-thiocarboxylic acids by biocatalytic dynamic kinetic resolution (DKR) of nitrile precursors exploiting nitrilase enzymes is described. A panel of 35 nitrilase biocatalysts were screened and enzymes Nit27 and Nit34 were found to catalyse the DKR of racemic α-thionitriles under mild conditions, affording the corresponding carboxylic acids with high conversions and good-to-excellent ee. The ammonia produced in situ during the biocatalytic transformation favours the racemization of the nitrile enantiomers and, in turn, the DKR without the need of any external additive base.

https://chemistry-europe.onlinelibrary.wiley.com/doi/pdf/10.1002/chem.202001108

Enantioselective Synthesis of α-Thiocarboxylic Acids by Nitrilase Biocatalysed Dynamic Kinetic Resolution of α-Thionitriles.

Biocatalysis is a branch of catalysis that exploits enzymes to perform highly stereoselective chemical transformations under mild and sustainable conditions. This Synpact highlights how biocatalysis can be used in the synthesis of chiral 1,3-mercaptoalkanols, an important class of compounds responsible for the flavours and aromas of many foods and beverages. The identification of two ketoreductase (KRED) enzymes able to reduce prochiral ketone precursors enantioselectively to 1,3-mercaptoalkanols bearing a C–O stereocentre is presented. In addition, the combination of a photocatalytic thia-Michael reaction to access prochiral ketones with subsequent KRED-biocatalysed reduction in a one-pot cascade is presented. Photo-biocatalysed cascades represent one of the new and most intriguing challenges in synthetic chemistry, because the combination of different catalytic methodologies in domino processes offers unique opportunities to outperform sequential reactions with a high degree of selectivity and the avoidance of the need to isolate reaction intermediates. 1 	Introduction 2 	Biocatalytic Synthesis of 1,3-Mercaptoalkanols 3 	Photo-Biocatalytic Synthesis of 1,3-Mercaptoalkanols 4 	Photo-Biocatalysed Cascade Reactions 5 	Conclusions

Kate Lauder

Papers

Synthesis and Reactivity of Propargylamines in Organic Chemistry

Photo-biocatalytic One-Pot Cascades for the Enantioselective Synthesis of 1,3-Mercaptoalkanol Volatile Sulfur Compounds

Design, Synthesis and Discovery of N,N'-Carbazoyl-aryl-urea Inhibitors of Zika NS5 Methyltransferase and Virus Replication.

Enantioselective Synthesis of α-Thiocarboxylic Acids by Nitrilase Biocatalysed Dynamic Kinetic Resolution of α-Thionitriles.

Photo-Biocatalytic Cascades for the Synthesis of Volatile Sulfur Compounds and Chemical Building Blocks