Articles in 2022

Synthesis of seven-membered carbocycles via (4 + 3)-cycloaddition reactions is often challenging due to the instability of the zwitterionic three-carbon component required. Now, a copper-catalysed enantioselective (4 + 3)-cycloaddition of 2-amino cations with dienol silyl ethers is reported, providing seven-membered carbocycles in good yields and with excellent enantiocontrol.

Anion-binding interactions are prevalent in nature but not commonly used in polymerizations. Now, an anion-binding catalytic strategy for living cationic polymerization is reported. Selenocyclodiphosph(V)azanes act as hydrogen-bond donors to reversibly activate dormant covalent bonds, and enable control of the equilibrium between the dormant and active species, which ensures precision polymer synthesis.

Controlling the enchainment of ether and carbonate segments during copolymerization of CO₂ and epoxides is rarely possible. Now, precise control of enchainment is realized by tuning the structure of an organoboron catalyst and the reaction conditions. Mechanistic and computational studies probe the origin of the unique ABB microstructure of the polymer.

Dual-atom catalysts are promising for CO₂ reduction reactions; however, sluggish kinetics limit practical applications. Now, a Ni dual-atom catalyst has been synthesized, realizing efficient electrocatalytic CO₂ reduction with a CO partial current density of ~1 A cm² at >99% Faradaic efficiency.

[10]annulene derivatives are typically non-planar and non-aromatic, with aromatic planar variants suffering from kinetic instability. Now, the synthesis of a planar and aromatic dehydro[10]annulene featuring a fused cyclopropane and an internal alkyne is reported. The resulting hydrocarbon is bench stable and can be stored for extended periods of time.

The integration of two-dimensional semiconductors and arbitrary materials or architectures offers the possibility to enhance the functionality of a material and improve device performance. Now, a general synthesis route is reported for heteroepitaxial growth of semiconducting 2H-MoTe₂ films on arbitrary single-crystal substrates and three-dimensional architectures without the limitation of lattice matching and a planar surface.

Preparing two-dimensional heterolayers by vertically stacking chemically different layers with multiple anions remains challenging. Now, a general approach for the synthesis of heterolayered oxychalcogenides using molten hydroxides as unconventional solutions for the rapid stacking of oxide and chalcogenide layers with precise composition control is demonstrated.

Quantum chemical calculations are typically used in synthetic organic chemistry to probe reaction mechanisms and propose stereochemical models. Now, a strategy to develop chemical reactions using quantum chemical calculations is reported. This study demonstrates in silico reaction screening with difluorocarbene, leading to a method for the synthesis of fluorinated N-heterocycles.

The performance of single atom catalysts (SACs) is controlled by the metal single atom sites, but the role of the matrix material is less understood. Now, a hard-template synthesis is reported, enabling control of the atomic and mesoporous structures of SACs and the probing of matrix materials with either 2D or 3D diffusion channels.

Functionalization of C–H bonds through direct hydrogen atom transfer (HAT) photocatalysis is an attractive synthetic reaction; however, many methods suffer from low catalytic efficiency. Now, the efficiency of direct HAT photocatalysis using photocatalyst eosin Y combined with Brønsted acids is reported, enabling the functionalization of unactivated C(sp³)–H bonds.

Inspired by molecular catenanes, mechanically interlocked gold nanocatenanes are synthesized starting from triangular gold nanoplates. The interlocked gold nanocatenanes have intriguing optical and mechanical properties, originating from their plasmonic nanomechanical bonds.

The construction of C–C bonds with regio- and stereoselectivity is paramount in natural product synthesis and metal-catalysed asymmetric allylic alkylation reactions have played a key role, with high C3 selectivity demonstrated in butenolide synthesis. Now, a palladium-catalysed C5-selective method is reported, providing direct and highly enantioselective access to a range of diversely substituted butenolides.

The synthesis of P-stereogenic allenylphosphine derivatives is often long or requires preformed P-stereogenic substrates. Now, a one-step enantioconvergent synthesis of allenylphosphines with both P and axial chirality is reported. The process proceeds through a Ni^II-catalysed propargylic substitution of secondary phosphines, without racemization or symmetrization of the racemic propargylic carbonates, to give P-stereogenic allenylphosphines.

The synthesis of noble metal chalcogenides (NMCs) in a well-controlled manner remains challenging. Now, a robust and versatile strategy for the preparation of a wide variety of NMCs via cation exchange is demonstrated and the generality of this strategy is validated by the synthesis of NMCs with tailored morphologies and compositions.

Atroposelective synthesis of C–N axially chiral anilides typically requires preformed aromatic ring systems. Now, a cobalt-catalysed atroposelective C–H activation and annulation method to construct isoquinolinones from benzamides, with C–N axially chirality, is reported. Using a chiral salicyl-oxazoline ligand and O₂ as an oxidant, the method yields isoquinolines in excellent yields and enantioselectivities.

The Mizoroki–Heck reaction forms C−C bonds between aryl halides and alkenes. For electron-deficient alkenes, β-coupled products are typically formed and synthesizing α-arylated products is challenging. Now, a triple catalysis system (nickel, photoredox catalysis and sulfinate) enables regioirregular formal Mizoroki–Heck reactions for electron-deficient alkenes and styrenes to give α-arylated alkenes.

Enantioselective C–H amination is an attractive strategy for the synthesis of chiral amines. Now, a combined radical and ionic approach has been developed for 1,2-difunctionalization of alcohols by merging enantioselective radical C–H amination with stereospecific nucleophilic ring-opening, enabling synthesis of β-functionalized chiral amines.

The high stability of THF and rapid cleavage of α-anionic THF make the direct generation and use of α-anionic THF challenging. Now, a flow synthetic method is used to control the metallation of unstable α-anionic THF, allowing a range of functionalization reactions to be carried out directly on THF.

Nature evolves diverse pathways for production of acetyl-CoA, a principal biosynthetic building block. Now, through in silico thermodynamic and kinetic analyses, this study proposes an acetyl-CoA biosynthetic route from C1 compounds and implements it in gas-fermenting bacteria for effective production of C2 metabolites.

Interlocking between non-trivial molecular knots provides a route to topologically complex mechanically interlocked molecules. Now, a topologically chiral prime link with 14 crossings is synthesized in a stereoselective manner through the quadruple interlocking of two homochiral trefoil knots.