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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 3d-metal-catalyzed β-C–H bond activation via 4-membered metallacycles remains an elusive challenge. Here, the authors report a Ni-Al bimetal-catalyzed β-C(sp3)–H bond activation of formamides via 4-membered nickelacycles.

Stereodivergent construction of non-adjacent stereocentres remains challenging in asymmetric synthesis, with prior examples limited to one cyclic or allenic stereocentre. Now it has been shown that Ni-catalysed migratory hydroalkylation of trisubstituted alkenes enables enantio- and diastereodivergent access to all four stereoisomers of acyclic molecules bearing remote 1,3- or 1,4-stereocentres.

Boron-stereogenic and C–B axially chiral compounds featuring boron-based chirality represent a rarely explored class of chiral scaffolds. Here, the authors report an asymmetric access to boron-stereogenic and C–B axially chiral (hetero)cycles via rhodium-catalyzed C–H activation of (hetero)arenes en route to [4 + 2] or [3 + 2] annulation with two classes of boron-functionalized alkynes.

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.

Enantioselective C—C activation remains heavily underexplored and has been predominantly limited to intramolecular reactions. Here the authors report two categories of asymmetric intermolecular [4+2] annulations between benzocyclobutenones and unsaturated reagents, namely, alkynes and cyclic dicarbonyl compounds.

In divergent carbonylative transformations using identical starting substrates, ligand-assisted transition metal catalysis has dominated selectively controllable transformations, but achieving precise control of CO insertion in transition-metal-free systems remains a challenge. Here, the authors disclose a divergent radical tandem carbonylation of multisubstituted homoallylic alcohols for the synthesis of γ-lactones and 1,4-diones.

The development of methods for conversion and utilization of amides has attracted much attention in organic synthesis and drug discovery. Herein, the authors report a divergent alkynylative difunctionalization of amides in a single transformation to generate either amines or alcohols through C–O or C–N cleavage.

The enantioselective synthesis of silicon-stereogenic vinylsilanes from simple alkenes remains underexplored. Here the authors report the enantioselective method from simple alkenes to yield linear silicon-stereogenic vinylsilanes with good yields and enantiomeric ratios under rhodium catalysis.

Biorenewable feedstocks are important for developing more sustainable materials, but developing processes can be challenging due to incompatible reaction conditions. Here, the authors report the one-pot preparation of aggregation-induced emission luminogens from lignin moieties.

The synthesis of urea by electrochemically converting the waste of nitrate and carbon dioxide is an interesting approach, but currently still restricted to low urea yield rate and Faradaic efficiency. Here, the authors report an efficient copper single-atom alloy electrocatalyst toward urea electrosynthesis.

Molecules with axial chirality are of intense focus to the synthetic organic community, but the axes most commonly explored are carbon–carbon and carbon–heteroatom. Here the authors report the syntheses of diaxially chiral biaryls containing N-N and C-N/C-C axes, achieved via rhodium catalysis.