Asymmetric synthesis articles from across Nature Portfolio

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.

Axially chiral indoles are crucial in synthetic and biological contexts, yet atroposelective halogenation remains underexplored. Here, the authors achieve catalytic and enantioselective iodination of N-arylindoles, utilizing a chiral phosphoric acid to control the C−N stereogenic axis.

The precise control over regio- and stereoselectivity from the same substrate represents a significant challenge in organic chemistry. Here, the authors present a switchable organocatalytic enantioselective carbosulfenylation/sulfenolactonization of cyclohexa-1,4- dienes to access chiral bicyclo[m.n.1] ring systems, which can be guided by tuning the substituent of the sulfenylating agent.

Achieving precise stereocontrol and sequence control over polymer microstructure is a formidable challenge in synthetic polymer chemistry. Catalyst modification has now enabled the stereo- and sequence-controlled polymerization of BDPO-based monomers (M) to afford isoenriched block polymers P(cis-M)-b-P(trans-M), which have tunable properties and can be converted back to monomers.

Benzosilacycles are of potential interest in drug discovery and materials science, and they are often synthesized through transition-metal cyclizations. Here, the authors report iron-catalyzed sequential hydrosilylations of alkynes to access various 5-, 6-, 7- and 10-membered benzosilacycles in high yield and selectivity.

Afucosylated antibodies, known for enhanced antibody-dependent cell cytotoxicity, require efficient production methods for broader application. Here, the authors explore three synthetic routes for β-L-carbafucose as a metabolic inhibitor of antibody fucosylation, achieving a chromatography-free synthesis, and demonstrating a multi-gram production of afucosylated Herceptin using β-L-carbafucose.

Enantioselective C(sp³)–H alkylation of easily accessible saturated heterocycles is challenging. Now, a nickel-catalysed enantioselective C(sp³)–H alkylation of saturated nitrogen and oxygen heterocycles with olefins has been developed, offering an efficient strategy for the stereoselective formation of C(sp³)–C(sp³) bonds.

Multicomponent couplings offer powerful approaches for rapidly increasing molecular complexity, but typically require functionally distinct reagents. Now, through dynamic combinatorial chemistry, structurally similar amino groups can be efficiently differentiated, enabling the enantioselective aminomethylamination of dienes to prepare 1,3-diamines.

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.

Directional interactions and three-dimensional functional groups are crucial to medicinal compounds. Consequently, new functional groups require stereocontrolled synthetic methods. Now, an enantiopure building block provides controlled and divergent access to valuable sulfonimidoyl functional groups.

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.

Stereoselective decarboxylative protonation can produce diverse chiral molecules from widely available carboxylic acids. However, general and practical strategies are lacking. Now, a chiral spirocyclic phosphoric acid-catalysed decarboxylation of aminomalonic acids has enabled the modular synthesis of α-amino acids.