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Thermodynamically disfavoured substituted cyclohexane compounds often display superior physical and bioactive properties to their isomeric counterparts. Now their synthesis is achieved by Ni-catalysed coupling of substituted methylenecyclohexanes with electrophiles under kinetic control.

The intricate, three-dimensional chain-walking of tertiary metal species has stood as a barrier to precision in migratory difunctionalization of multisubstituted alkenes. Now a sterically controlled chain recognition paradigm has been established, enabling highly selective head–tail carboboration and offering a streamlined route to natural products and functional materials.

Difunctionalization of alkenes can afford useful building blocks from readily available starting materials, but these reactions often show limitations in olefin scope. This work presents a catalyst-controlled enantioselective 1,1-arylboration of unactivated alkenes that is independent of directing groups.

Creating glycoside building blocks with multiple diversifiable positions from readily available sugar precursors remains a challenging task. Herein, the authors present a regio- and stereoselective nickel-catalyzed carboboration of glycals, which offers a platform for generating glycoside diversity with diverse C1 and C2 modification potential.

The transition metal-catalysed multicomponent cross-coupling of alkenes currently relies on strongly coordinating groups to direct the reactivity. Now Wu et al. present a nickel catalyst that enables the installation of sp² and sp³ fragments on alkenes using alcohols and ethers as directing groups.

Multicomponent cross-coupling of alkenes with silicon reagents is used to yield complex silicon-containing compounds from readily accessible feedstock chemicals but the reaction with simple alkenes remains challenging. Here, the authors report a regioselective silylalkylation of simple alkenes, which is enabled by using a stable Ni(II) salt and an inexpensive trans-1,2-diaminocyclohexane ligand as a catalyst.

Alkene 1,1-difunctionalization can provide direct access to valuable molecules. Now, an organometallic-radical relay strategy involving radical generation through homolysis of the metal–alkyl complex allows catalytic coupling of terminal or internal alkenes with arylboronic acids and electrophilic radical acceptors.

The potential of leveraging diverse geometric configurations of the catalysts to achieve divergent synthesis remains largely untapped. Here, the authors report a stereodivergent three-component borylfunctionalization of alkynes, enabled by ligand-modulated geometric variations in nickel catalysts.

Migratory cross-coupling reactions are powerful tools to form bonds at predictable positions. Here the authors report a nickel-catalyzed migratory Suzuki–Miyaura cross-coupling of unactivated alkyl electrophiles with aryl and vinyl boron reagents and provide experimental and computational mechanistic evidence.

The synthesis of thermodynamically disfavoured substituted six-membered rings provides a notable challenge compared with that of the thermodynamically stable stereoisomer counterparts. This Review provides a summary of current strategies for their synthesis.