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The construction of all stereoisomers of molecules containing contiguous stereocentres with full control of the absolute and relative stereochemical configuration has rarely been demonstrated. An approach involving dual-catalytic activation enables the stereodivergent α-propargylation of oxindoles with high stereocontrol and shows broad substrate scope.
Reductive coupling reactions mediated by samarium(ii) iodide are useful transformations to form C–C bonds. The unique reactivity and selectivity of SmI2 result in its wide application in key steps in the total synthesis of natural products. This Review outlines synthetic routes using this versatility to make important C–C bonds in complex products.
Ring-forming reactions are at the heart of organic synthesis. Now, phenylene rings are synthesized from two isopropyl moieties on a gold surface. Resolving the intermediates of this (3+3) cycloaromatization reaction with atomic force microscopy offers mechanistic insight into the dimerization process.
A method for the synthesis of sterically congested α-amino acids and peptides using amino acid Schiff bases and hydrocarbons is developed. A superior helix-stabilizing effect of highly congested unnatural α-amino acids is demonstrated by circular dichroism measurements of synthesized peptides.
By showcasing the activating effect of using alkali-metal alkoxides as additives with polar organometallic reagents, this Perspective outlines applications of these mixed-metal combinations for arene functionalization via metal/halogen exchange and deprotonative metallation. Our mechanistic understanding of how these systems operate has revealed their complex and diverse mixed-metal/mixed-aggregate composition.
Cascade dearomative cyclization reactions are an important subclass of catalytic asymmetric dearomatization reactions, for the synthesis of polycyclic scaffolds. In this Review, cascade asymmetric dearomative cyclization reactions which are catalysed by transition-metal complexes are discussed, with a focus on the cyclization of indoles and related heteroaromatic compounds.
‘Solar chemical’ production can be limited by the need for sacrificial reagents, metal-containing catalysts and low product values. Now, H2O2 is generated from H2O and air using lignin as a photocatalyst. Combining lignin with enzymatic catalysis enables selective oxyfunctionalization.
Inorganic nanocrystals coated with surfactant-like organic molecules have a vast range of properties arising from the combination of their components. In this Review, the role of the organic ligands on the synthesis of colloidal nanocrystals is discussed with a focus on the tails of the ligands and their collective effects on the surface.
Boronic esters are versatile intermediates that readily accept nucleophiles and then undergo 1,2-migration, expelling a neighbouring leaving group. Such reactivity enables carbon chains to be grown one atom at a time with high stereocontrol. This Review examines the fundamentals of lithiation–borylation methodology and its application to natural product synthesis.
During the liquid-to-solid transition of alloys with very small concentrations of a minor component, surface patterns emerge that feature enrichment of the minor component. These periodic surface patterns may be beneficial for the use of precious metals in surface science applications.
The α-arylation of ketones is a powerful synthetic strategy for the construction of C–C bonds, but general metal-free methods are scarce. Now, a green-light-mediated photoredox protocol enables this transformation, giving access to a broad range of useful building blocks and value-added biorelevant products.
Asymmetric cyanation reactions promoted by chiral copper catalysts via a radical relay process are discussed in this Perspective. In particular, we outline the mechanisms of carbon radical formation and subsequent asymmetric radical cyanation reactions.
Predictably activating C–H and C–C bonds for the synthesis of new materials remains a challenge within the synthetic community. A ternary catalytic dance between radicals, metals and light may unlock this puzzle.
Late-stage tritiation with high selectivity, isotopic purity and functional-group tolerance is important for the radiolabelling of drug candidates or bioactive compounds. Now, a broadly applicable protocol using aryl thianthrenium salts allows for tritiation of complex molecules by hydrogenolysis via an intermediate cationic palladium complex.
Iterative synthesis can generalize, automate and democratize the molecule-making process. Now, by using a computer algorithm to scan the depths of chemical reactivity space, thousands of iterative ways to make small molecules are discovered.
Enzymes catalyse reactions with unparalleled activity and selectivity. Using chemical insights, researchers can now direct these powerful natural catalysts to perform new-to-nature transformations that solve challenging synthetic problems. In this Perspective, we show how chemists and protein engineers have guided nature’s genetically encoded and evolvable machinery to perform new biocatalytic transformations.
Remote functionalization through alkene isomerization is a popular strategy in organic synthesis. The dynamic nature of alkene isomerization typically leads to difficulties in controlling the stereochemistry of C(sp3) centres along the carbon skeleton. This Review outlines synthetic methods that tackle this issue and leverage alkene isomerization to control C(sp3) stereocentres in complex organic molecules.
Oximes are valuable motifs with diverse reactivity. This Review outlines the breadth of oxime reactivity including N–O bond fragmentation through transition metal catalysis and photocatalysis, [2 + 2]-cycloaddition reactions, asymmetric reduction and applications in materials science. Developments in transition metal catalysis and photocatalysis highlight the use of oximes as powerful synthetic building blocks.
