Asymmetric catalysis articles from across Nature Portfolio

Chiral amines possessing a stereogenic carbon atom bearing three carbon substituents and one nitrogen substituent are challenging structural motifs to prepare enantioselectively. Now, such motifs have been accessed in high enantiopurities by asymmetric Cu-catalysed propargylic amination using sterically confined ligands.

The stereospecific Z/E isomerization of tetrasubstituted alkenes remains underdeveloped, thus lacking in a stereodivergent synthesis of axially chiral alkenes. Here, authors report the atroposelective synthesis of tetrasubstituted alkene analogues by asymmetric allylic substitution-isomerization, followed by the photocatalyzed Z/E isomerization.

Planar chiral [2.2]paracyclophanes have a wide range of applications in asymmetric synthesis and materials science. However, they are accessed via time-consuming chiral separations or kinetic resolution approaches. Here, the authors report a simple, metal-free protocol for organocatalytic desymmetrization of prochiral diformyl[2.2]paracyclophanes.

The redox properties of visible-light-absorbing photosensitizers are limited by the energy of visible photons, but methods using sensitization-initiated electron transfer have recently been developed to address these challenges. Now a multiphoton dual-catalyst strategy has been used to enable the enantioselective de Mayo reaction for the synthesis of enantioenriched 1,5-diketones.

P-stereogenic heterocycles are privileged chiral ligands and bioactive compounds, but the catalytic asymmetric synthesis of P-stereogenic phosphindane derivatives is challenging. Here, the authors report a catalytic kinetic resolution of phosphindole oxides via rhodium-catalyzed diastereo- and enantioselective conjugate addition to access enantiopure Pstereogenic phosphindane and phosphindole derivatives.

Enantioenriched α-disubstituted α-ethynylamines are valuable synthons to chiral α-tertiary amines and azacycles, but their facile access remains challenging. Now, sterically confined pyridinebisoxazoline ligands have been developed to facilitate highly enantioselective Cu(I)-catalysed propargylic amination of both aliphatic and aryl ketone-derived propargylic carbonates to give α-tertiary ethynylamines. Related tandem sequences are reported to synthesize quaternary azacycles.

Planar-chiral cyclophanes are important for drug discovery but the enantioselective synthesis of planar-chiral cyclophanes remains challenging. Here the authors describe an N-heterocyclic carbene-catalyzed asymmetric construction of planar-chiral cyclophanes.

Chiral amines possessing a stereogenic carbon atom bearing three carbon substituents and one nitrogen substituent are challenging structural motifs to prepare enantioselectively. Now, such motifs have been accessed in high enantiopurities by asymmetric Cu-catalysed propargylic amination using sterically confined ligands.

Ciro Romano, Jack I. Mansell, and David J. Procter have explored the versatility and selectivity of samarium diiodide, and its use as a radical relay catalyst.

Chiral BINOL-phosphates have qualified as privileged Brønsted acid organocatalysts, providing solutions to many challenging enantioselective transformations for a wide range of substrates under mild reaction conditions. Here we revisit the story of their origins.

The direct carbonylation of alkanes with CO suffers from low conversion owing to equilibrium constraints. Now, a strategy is presented that combines reversible alkane carbonylation with an asymmetric transformation to overcome the equilibrium limitations, enabling the synthesis of chiral β- and α-amino ketones from alkanes, CO and anilines.

Tetracoordinate boron molecules are the key intermediates in many organoboron-related chemical transformations. Now, using alkynyl tetracoordinate boron species, a nickel-catalysed asymmetric 1,3-metallate shift towards axial chirality has been developed, giving access to various axially chiral alkenes in high efficiency.

Palladium-catalysed enantioselective α-arylation of azlactones and 5H-oxazol-4-ones with aryl halides using Sadphos ligands enables the synthesis of α-aryl quaternary amino acids and glycolic acid derivatives.