Themed collection New reactivity in organic chemistry

Andrei Yudin and Corinna Schindler introduce the Chemical Science themed collection on the topic of new reactivity in organic chemistry.

Hydrogen atom transfer from metal hydrides to alkenes appears to underlie widely used catalytic methods – the mechanistic implications are fascinating.

This perspective on reactivity introduces Synthetic Half-Reactions (SHRs) as a way to analyze chemical transformations.

This perspective provides insight into recent electro-organic methods and general trends in this field, and opens up prospects for future viewpoints.

Cubane has attracted attention due to its unique 3D structure. Herein, we report the programmable synthesis of multiply arylated cubanes. The developed reaction allows the late-stage and regioselective installation of aryl groups.

The venerable Hauser–Kraus annulation is an effective and convergent method for generating oxygenated polycyclic aromatic compounds. A catalytic Hauser–Kraus annulation has been developed based on N-heterocyclic carbene catalysis.

An intramolecular C(sp³)–H amidation proceeds in the presence of t-BuOK, molecular oxygen, and DMF.

The selective 1,2-aminoacylation of olefins provides opportunities for the rapid construction of nitrogen-containing molecules.

Endo-pyramidalisation at nitrogen bestows enamines derived from α-substituted amines with higher reactivity compared to exo-pyramidalisation.

Brønsted acids can catalyze triplet energy transfer reactions, and DFT computations suggest the unexpected importance of reorganization energy for catalysis.

Amine-anchored sulfamides direct radical-mediated chlorination of aliphatic C–H bonds. The site of C–H abstraction can be modulated by varying the sulfamide nitrogen substituents, a feature that has not been demonstrated with other substrate classes.

Studies of S-linked glycoconjugates have attracted growing interest because of their enhanced chemical stability and enzymatic resistance over O-glycoside counterparts.

The oxidative coupling of alkyltrifluoroborates with heteroatom-tethered vinylarenes leads to a broad range of saturated oxygen and nitrogen heterocycles.

The mechanism of the gold-catalyzed oxidative cross-coupling of arenes and alkynes has been studied in detail combining stoichiometric experiments with putative reaction intermediates and DFT calculations.

In this manuscript, we describe the conversion of fuscol, a natural product isolated in 1978, to xishacorenes A, B, and C, isolated in 2017, as well as a previously unreported congener, which we have named xishacorene D.

Through rational evaluation of ligands and promoters, the reactivity of a key Pd(II) species towards transmetalation or β-H elimination is manipulated.

Chiral phosphoric acid catalyzed the formal [4+2]-cycloaddition of 2-benzothiazolimines with enecarbamates to provide benzothiazolopyrimidines with up to 99% yield and >99% ee.

Herein, we report the radiosynthesis of ¹⁸F-difluoromethylarenes via the assembly of three components, a boron reagent, ethyl bromofluoroacetate, and cyclotron-produced non-carrier added [¹⁸F]fluoride.

A modular synthesis of enantioenriched polyfunctionalized cyclobutanes was developed and applied to the synthesis of (+)-rumphellaone A.

A radical relay strategy has been developed to enable selective δ C–H arylation. The approach employs a chiral copper catalyst, which serves the dual roles of generating an N-centered radical to promote intramolecular H-atom transfer, and then intercepting a distal C-centered radical for C–C bond formation with (hetero)aryl boronic acids.

Synthetic chemists have spent considerable effort optimizing the synthesis of nitrogen and oxygen containing compounds through a number of methods; however, direct introduction of N- and O-functionality remains challenging.

A practical metal-free perfluoroalkylation using acid anhydrides with unique reaction mode via carbocation has been developed.

An unusual example of π-acid catalyst-dependent selectivity in the cycloisomerization of alkene-tethered sulfonium ylides affords cyclopropanes or dihydrofurans with excellent control of chemoselectivity.

By controlling the stability of dynamic covalent crosslinks with adjacent photoswitches, the stiffness of an adaptable hydrogel is tuned reversibly.

A novel regio- and stereocontrolled macrocyclization strategy was developed for the first synthesis of ceanothine D.

Replacing the O-linked saccharide in the bacteriocin glycocin F with an S-linked version results in a peptidomimetic that increases the bacteriostatic effect.

Ni-catalysed diarylation of vinylpyridylsilanes with arylzinc reagents and aryl halides is reported by stabilizing Heck intermediates as pyridylsilyl-coordinated transient metallacycles.

A mechanistic study of the Pd-catalyzed intramolecular addition of carbamoyl chlorides and aryl halides across alkynes is presented.

An enantioselective, redox-relay Heck alkenylation of trisubstituted allylic alkenol substrates has been developed.