Themed collection 2022 Organic Chemistry Frontiers HOT articles

An acyclic arsine catalyst has been developed for the room-temperature catalytic arsa-Wittig reaction. The reaction mechanism has been computationally analyzed.

Vinyl cyclic carbonates undergo an exo-cyclic attack by thiol nucleophiles under DBU catalysis to form allylic thioether products in moderate to good yields through a decarboxylative process under attractive process conditions.

We herein report an efficient and green aerobic radical cascade reaction of o-vinylphenylisocyanides with thiols to access a broad range of 2-thio-substituted quinolines without the need for additional catalysts or oxidants.

We have developed a base mediated formamidation of amines with CO under mild conditions, which allows for the synthesis of a wide range of aromatic and aliphatic formamides in high yields and gram amounts in the absence of a transition metal.

A palladium-catalyzed enantioselective domino ring-opening/Hiyama coupling of cyclobutanones is reported, providing chiral 1-indanones bearing a versatile alkenyl group.

The highly selective and scalable dehydrogenative hydroxylation of hydrosilanes, featuring a low loading of the Earth-abundant cobalt catalyst, water as the green oxidant, and good generality for various hydrosilanes, is reported.

An efficient synthesis of methylene-unsubstituted cyclopropane-fused indolines via photoredox catalyzed dearomative cyclopropanation of indole derivatives was developed.

An efficient photoactive charge transfer complex protocol for the (alkoxycarbonyl)methylation reaction of alkenes with phosphonium salts is established.

1,3-N,Si-Tetraorganosilane reagents TsHNCH₂SiBnR¹R² were developed as robust synthons to prepare 3-silaindolines via a Cs₂CO₃-promoted (3 + 2)-annulation reaction with arynes.

The cobalt(II)-catalyzed C–H bond acyloxylation of picolinamides with bifunctional silver carboxylate has been developed. The mild and practical esterification provides an atom-economic route to access to polysubstituted naphthalene compounds.

A simple and sustainable KI-mediated electrochemical enantioselective dihydroxylation reaction for the synthesis of chiral acyclic nucleosides was developed for the first time with only a 0.1 mol% Os catalyst.

Disarming the alkoxide trap using an in situ reduction strategy to access a practical FeCl₃ and N-heterocyclic carbene system for borrowing-hydrogen N-alkylation.

A photoredox approach was reported to realize a highly selective three-component thiohydroxylation, thioalkoxylation and thioamination of vinylarenes towards valuable vicinal S,O- and S,N-disubstituted molecules under mild conditions.

A formal total synthesis of dankasterone B was achieved in 15 steps.

An asymmetric IEDDA reaction of 2-pyrones with indenes catalyzed by a chiral N,N′-dioxide/Ni(OTf)₂ complex has been disclosed to construct highly functionalized hexahydrofluorenyl bridged-lactone scaffolds in high yields and ee.

Chiral aggregates of achiral aza-BODIPY 1 was obtained in a nearly achiral medium, i.e. a limonene/MCH mixed solvent with a chiral limonene ratio <1% (v/v), by living supramolecular polymerization exploiting the chirality memory of dye 1 aggregates.

The first total synthesis of two macrocyclic Lycopodium alkaloids, huperserratines A and B, in 12 steps.

An efficient Brønsted acid (BA) catalyzed intramolecular dearomatization cyclization of naphthol-ynamides has been developed, enabling the practical and divergent synthesis of two azaspirocycles in high yields.

By using a robust aminoazanium reagent H₂N-DABCO, a momentary clicking nitrile synthesis from aldehyde and various adehyde precursors was achieved.

A novel decarboxylative cyclization of o-chlorobenzoic acids with C,C-palladacycles formed by an aminopalladation/dealkylation strategy for the assembly of dibenzo[a,c]carbazoles has been reported.

An automated machine-aided solid phase synthesis of heparan sulfate (HS) has been established for the first time. With the significantly reduced number of synthetic and purification steps, 16 HS disaccharides have been readily assembled.

A highly efficient transition-metal-free radical cyclization route for the synthesis of oxindoles was developed, using the readily available 9,10-phenanthrenequinone (PQ) catalyst together with K₂CO₃.

Asperflavipines C–E, three new cytochalasin heterotetramers, possessing a highly complex tetradecacyclic ring system with continuous bridged ring systems, and aspermichalasine A, possessing an unusual 5/6/5/8 ring system, were isolated.

The first asymmetric total synthesis of (–)-arbophyllidine, an unusual pentacyclic monoterpenoid indole alkaloid, has been achieved.

A concise total synthesis of opioids is presented. The development of a regioselective Pd-catalyzed dearomatization arene coupling that requires no additional blocking groups allows for efficient access to a common thebaine core.

A diastereoselective cycloaddition of bicyclo[1.1.0]butanes (BCBs) with triazolinedione or nitrosoarenes was developed to access multi-substituted cyclobutanes.

We present a new family of oxindole-based functionalised at three positions on the upper and lower halves, with methoxy or cyano groups. We find that this allows the absorption wavelength and quantum yields of these motors to be tuned.

A new HAT-initiated C(sp³)–C(sp²) bond cleavage approach enabling the functionalization of alkenes to ketones is presented.

An enantioselective olefinic C–H alkenylation using transient group was disclosed to afford axially chiral aryl 1,3-dienes in up to 99% yields and up to >99% ee. The derived carboxylic acid was efficient ligand in asymmetric C–H alkylation.

The novel unimolecular Ir-Ni bimetallic system with the conjugated bridging ligand has been developed. Photoinduced cross-coupling reactions (C–O, C–S, C–N) demonstrated the enormous potential of a conjugately bridged Ir–Ni catalytic system.

A series of novel chiral pyridine-oxazolines were synthesized via catalytic asymmetric Heine reaction of meso-N-(2-picolinoyl)-aziridines.

Chiral phosphoric acid has been utilized for covalent activation of propargylic alcohols to act as pre-catalyst. With this activation mode, a range of highly regio- and enantioenriched heterocyclic products could be generated efficiently from racemic propargylic alcohols.

A novel S-induced Schmidt-type rearrangement of vinyl azides with CF₃SO₂Na is developed for synthesis of N-arylated 2-(trifluoromethylsulfinyl)acetamieds, which is mediated by triphosgene (BTC) under mild reaction conditions.

Organocatalytic atroposelective construction of axially chiral nonsymmetric biaryltriols and their applications in asymmetric synthesis and heavy metal ion detection.

The synthesis of β-azidosulfones starting from alkenes, cycloketone oxime esters, trimethylsilyl azide and a sulfur dioxide surrogate of DABCO·(SO₂)₂ under iron catalysis is developed.