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The selective removal of one oxygen atom from sulfones, without over-reduction to sulfide, is a challenging task. Now, through organocatalysis and incorporation of a cyano group into the sulfone, an asymmetric deoxygenation strategy has been developed, providing an efficient method for the synthesis of chiral sulfinyl compounds.
Amilra Prasanna (AP) de Silva talks to Nature Chemistry about his path in chemistry, from photochemistry to sodium sensors to logic gates, through connections between people and between two places that share more than it may seem, Sri Lanka and Northern Ireland.
Interlocking macrocyclic carbon nanomaterials is an exciting way to tune their molecular properties, but all-conjugated catenanes and rotaxanes are extremely challenging to make. Now, fully π-conjugated [2]- and [3]catenanes as well as a [3]rotaxane have been prepared through an ‘active metal template’ approach.
Neutral homoaromatic hydrocarbons—which possess an interrupted π-system yet display aromatic properties owing to through-space or through-bond interactions—have remained rare as they are typically unstable. Now a class of stable neutral homoaromatic homoannulenes has been synthesized, including one that acts as a photoswitch through a reversible [1, 11] sigmatropic rearrangement.
Current strategies for photoinduced olefin metathesis lack wavelength tunability. Now, plasmonic nanoparticles have been used to activate latent ruthenium catalysts, enabling light-induced olefin metathesis in the infrared range with several advantages when compared with conventional heating. Implementing this approach in ring-opening metathesis polymerization resulted in photoresponsive polymer–nanoparticle composites with enhanced mechanical properties.
Mechanochemical generation of dyes with different photophysical properties generally requires the use of discrete mechanophore derivatives with unique chemical structures. Now it has been shown that diverse donor–acceptor Stenhouse adducts can be produced via a mechanically gated chromogenic reaction, enabling mechanochemical multicolour lithography.
Cycloaddition reactions are among the most useful reactions in chemical synthesis, but biosynthetic enzymes with 2 + 2 cyclase activity have yet to be observed. Now it is shown that a β-barrel-fold protein catalyses competitive 2 + 2 and 4 + 2 cycloaddition reactions. This protein can be engineered to preferentially produce the exo-2 + 2, exo-4 + 2 or endo-4 + 2 product.
The direct conversion of sulfones to chiral sulfinyl compounds is one of the major challenges in the fields of asymmetric synthesis and organosulfur chemistry. Now, through incorporation of a cyano group into the sulfone, an organocatalytic asymmetric deoxygenation strategy has been developed that enables the synthesis of chiral sulfinyl compounds.
An active-template approach has been used to prepare π-conjugated interlocked nanocarbons derived from [n]cycloparaphenylenes. A metal ion bound within the central cavity of a precursor macrocycle first catalyses cross-coupling reactions and then the resulting mechanically interlocked intermediates are further transformed into π-conjugated species—[2] and [3]catenanes as well as a conjugated [3]rotaxane.
A Diels–Alderase that catalyses the inherently disfavoured cycloaddition and forms a bicyclo[2.2.2]diazaoctane scaffold with a strict α-anti-selectivity has now been discovered. This Diels–Alderase, called CtdP, is an NmrA-like protein. Isotopic labelling, structural biology and computational studies reveal that the CtdP-catalysed Diels–Alder reaction involves a NADP+/NADPH-dependent redox mechanism.
Controlling various selectivities in radical reactions presents both formidable challenges and great opportunities. Now, Co(II)-based metalloradical catalysis has enabled the concurrent control of multiple convergences and selectivities in intermolecular radical allylic C−H amination. The reaction provides access to valuable chiral α-tertiary amines directly from an isomeric mixture of alkenes.
Ribosomes cannot synthesize peptides using hydroxy acids to replace canonical amino acids as no codons encode hydroxy acid building blocks. Now, this challenge has been addressed by rewriting the genetic code, enabling the direct cellular biosynthesis of non-natural depsipeptides containing non-canonical amino acids.
Molecular computing programmed with complementary nucleic acid strands allows the construction of sophisticated biomolecular circuits. Now, systems with partially complementary strands have been shown to enable more compact and faster molecular circuits, and may illuminate biological processes.
Introduced in response to growing numbers of scientists and conferences, posters gave an outlet to those not invited to give oral presentations. But why are poster sessions still the purview of students?
Interactions between proteins and non-proteinaceous biopolymers are essential for life; however, many methods used to characterize these interactions lack precision and display significant biases. Now, a genetically encoded method employing sulfur(vi) fluoride exchange (SuFEx)-based chemical crosslinking has been developed for capturing and analysing protein–RNA and protein–carbohydrate interactions in vivo.
The complementarity of the two strands in the DNA double helix provides a mechanism for the storage and processing of genetic information. Now, an alternative ‘strand commutation’ mechanism of data processing with DNA/RNA has been revealed based on the reversible low-affinity interactions of essentially non-complementary nucleic acids.
Principles of quantum interference can guide the design of chromophores that undergo singlet fission. Now, ‘pencil and paper’ graphical models can be used to understand and predict the dynamics of triplet pairs generated through singlet fission in bridged dimers.
Asymmetric systems for catalytic carbohydrate functionalization are mostly limited to chiral copper complexes and organocatalysts. Now, a synergistic chiral Rh(I)- and organoboron-catalysed site-selective functionalization of carbohydrate polyols has been developed, giving stereocontrolled access to biologically relevant arylhydronaphthalene glycosides. Enantio-, diastereo-, regio- and anomeric control and dynamic kinetic resolution were found to be concomitantly operative.
