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Enantioselective dicarbofunctionalization of alkenes is a powerful strategy for constructing functionalized sp³-rich molecules. Here, the authors report a palladium-catalyzed asymmetric migratory process that enables highly selective 1,3- and 1,4- diarylation of unactivated trisubstituted alkenes.

The linear-selective allylic addition to carbonyls remains challenging owing to the inversion of the six-membered transition state. Now an enantio- and linear-selective allylic addition to ketimines using reductive cobalt catalysis is reported. The process proceeds via a stereoselective radical pathway, forming homoallylic amino esters with excellent enantioselectivity and broad functional group tolerance.

The development of carbonylative reactions with CO gas under mild conditions are important in organic synthesis. Here, the authors demonstrate an earth-abundant nickel-catalyzed three-component tandem acylzincation/cyclization sequence of allene and alkylzinc reagent with 1 atm of CO.’

Six-membered chiral lactams are common structural motifs of pharmaceuticals. Here, the authors describe a nickel-catalyzed reductive carbamoylation of alkenes to form enantioenriched six-membered lactams.

In contrast to the well-established palladium-catalyzed version, the nickel-catalyzed carbonylative coupling is underdeveloped. Here the authors report a nickel-catalyzed allylic carbonylative coupling with alkyl zinc reagents, allowing for preparation of β,γ-unsaturated ketones in a linear-selective fashion.

The construction of vicinal stereocentres—particularly sterically bulky quaternary motifs—from racemic alkyl halides remains a formidable challenge. Here, a cobalt-catalysed enantioconvergent reductive addition of racemic alkyl halides to imines has been developed, enabling efficient synthesis of diverse contiguous stereocentres, including tertiary–tertiary, tertiary–quaternary and quaternary–quaternary stereocentres, with high diastereo- and enantioselectivities.

Saturated N-heterocycles are ubiquitous structures among natural products and biologically active compounds, but methods to edit the ring size of these substructures are scarce. Now the ring expansion of unactivated cyclic amines has been achieved via sequential Ru-catalysed C‒C bond formation, retro-aza-Michael addition and a lactamization process to construct synthetically challenging medium-sized azacycles.

Robust protocols for the synthesis of chiral α-tertiary amino acids remain scarce due to the challenge of constructing congested tetrasubstituted stereocentres. Now a cobalt-catalysed enantioselective aza-Barbier reaction of ketimines with various unactivated alkyl halides has been developed, forming diverse chiral α-tertiary amino esters with high enantioselectivity and excellent functional group tolerance.

The use of acyl functional groups as nucleophilic synthons in transition metal-catalysed carbometallation of unsaturated hydrocarbons remains challenging. Here, nickel-catalysed acylzincation reactions of alkynes and alkenes with organozinc reagents under 1 atm of CO are developed, featuring high functional group tolerance, a broad substrate scope and mild conditions.

Multi-iron nitrides are implicated as potential key intermediates in biological nitrogen fixation and the industrial Haber–Bosch process, but well-described functional model systems are rare. Now, a well-defined thiolate-bridged Fe^IVFe^IV μ-nitrido complex has been found to show excellent reactivity toward hydrogenation with H₂ through a stepwise pathway to form ammonia in high yield.

Although it is achieved routinely by nitrogenases, the conversion of molecular dinitrogen into ammonia under ambient conditions is proving difficult with synthetic systems. A thiolate-bridged diiron complex has now been developed that produces ammonia from coordinated N₂H₂ through a sequence of reduction and protonation reactions that may well mimic the biological nitrogen fixation.

This paper reports the genome sequence of domesticated tomato, a major crop plant, and a draft sequence for its closest wild relative; comparative genomics reveal very little divergence between the two genomes but some important differences with the potato genome, another important food crop in the genus Solanum.