Asymmetric catalysis articles from across Nature Portfolio

Enantioenriched alkyl–alkyl bonds are produced from abundant alkenes in one step via Ni-catalysed asymmetric cross-hydrodimerization. This technique overcomes the reactivity and selectivity challenges associated with coupling between two similar nucleophiles.

Boron dipyrromethenes (BODIPYs) have found widespread applications owing to their spectroscopic and photophysical properties, but strategies for the synthesis of enantioenriched boron-stereogenic BODIPYs are lacking. Now a modular enantioselective assembly of multi-substituted boron-stereogenic BODIPYs via a Pd-catalysed desymmetric Suzuki coupling has been developed, giving access to a range of highly functionalized chiral BODIPYs.

Catalytic asymmetric hydroboration of unsaturated bonds is the most straightforward method for the construction of chiral organoboron compounds but enantioselective hydroboration of allenes is challenging. Here, the authors report a cobalt-catalyzed asymmetric dihydroboration of allenes using a ligand relay strategy with two simple ligands to obtain chiral 1,4-diboronate products.

The absence of catalytic asymmetric methods for synthesizing chiral (hetero)bicyclo[n.1.1]alkanes has hindered their application in new drug discovery. Herein the authors report an enantioselective formal (3 + 3) cycloaddition of bicyclobutanes with nitrones using a chiral Lewis acid catalyst for the synthesis of hetero-bicyclo[3.1.1]heptane.

Sulfilimines are a class of chiral molecules that bear S(IV) stereocentres, which are of high value in drug discovery but difficult to synthesize. Now the authors report a chemo- and enantioselective Chan–Lam S-arylation of sulfenamides with arylboronic acids that delivers diaryl and alkyl aryl sulfilimines.

The catalytic enantioselective synthesis of inherently chiral calix[n]arenes with high enantiopurity has long been a challenging endeavor. Herein, the authors report an enantioselective cobalt-catalyzed C–H activation/annulation for the efficient construction of inherently chiral calix[4]arenes bearing multiple C–N axially chiral element.

Monofluoroalkenes serve as nonhydrolyzable mimetics of amides and are frequently encountered in drug candidates. Herein, the authors report a regio-, enantio-, and stereoselective NiH-catalyzed ipso- and migratory defluorinative olefin cross-coupling employing readily available olefins and gem-difluoroalkenes under mild conditions.

Enantioenriched alkyl–alkyl bonds are produced from abundant alkenes in one step via Ni-catalysed asymmetric cross-hydrodimerization. This technique overcomes the reactivity and selectivity challenges associated with coupling between two similar nucleophiles.

The development of enantiospecific sulfone reactions has been hindered by the inherent acidity of sulfones, which result in deleterious racemization. Now, the synthesis of enantioenriched diarylalkanes has been reported via sufficiently fast cross-coupling that circumvents racemization of the chiral sulfone.

An artificial metalloenzyme based on streptavidin with a biotinylated Rh(III) cofactor provides enantioselective access to various isoindolones with different functional groups. Rational engineering of the streptavidin scaffold reverses the stereoselectivity, offering an enantiodivergent method for the synthesis of isoindolones.

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.