Chiral trivalent phosphorus species are the dominant class of ligands and the key controlling element in asymmetric homogeneous transition-metal catalysis. Here, novel chiral diaminophosphine oxide ligands are described. The arising catalyst system with nickel(0) and trimethylaluminum efficiently activates formamide C-H bonds under mild conditions providing pyrrolidones via intramolecular hydrocarbamoylation in a highly enantioselective manner with as little as 0.25% mol catalyst loading. Mechanistically, the secondary phosphine oxides behave as bridging ligands for the nickel center and the Lewis acidic organoaluminum center to give a heterobimetallic catalyst with superior reactivity.

Metal-catalyzed functionalizations at the ortho position of a directing group have become an efficient bond-forming strategy. A wide range of transformations that employ Cp*Rh(III) catalysts have been described, but despite their synthetic potential, enantioselective variants that use chiral versions of the Cp* ligand remain scarce (Cp*=pentamethyl cyclopentadienyl). Cyclopentadienyl compounds with an atropchiral biaryl backbone are shown to be suitable ligands for the efficient intramolecular enantioselective hydroarylation of aryl hydroxamates. Dihydrofurans that bear methyl-substituted quaternary stereocenters are thus obtained by CH functionalization under mild conditions.

The 1,6-annulated 2-pyridone motif is found in many biologically active compounds and its close relation to the indolizidine and quinolizidine alkaloid core makes it an attractive building block. A nickel-catalyzed C-H functionalization of 2-pyridones and subsequent cyclization affords 1,6-annulated 2-pyridones by selective intramolecular olefin hydroarylation. The switch between the exo- and endo-cyclization modes is controlled by two complementary sets of ligands. Irrespective of the ring size, the regioselectivity during the cyclization is under full catalyst control. Simple cyclooctadiene promotes an exo-selective cyclization, whereas a bulky N-heterocyclic carbene ligand results in an endo-selective mode. The method was further applied in the synthesis of the lupin alkaloid cytisine.

he increase in antibiotic resistance raises concerns that, at least in some regions, we are returning to a pre-antibiotic era, in particular for Gram-negative infections. The increased prevalence of extended-spectrum serine-β-lactamases (SBLs) and metallo-β-lactamases (MBLs) means β-lactams are increasingly ineffective in treating Gram-negative infections 1,2 . The advent of mobilized colistin resistance-1 in 2015 3 and transferable tigecycline resistance genes (tetX3-tetX5) in 2019 4 , which mediate resistance to colistin and tigecycline, respectively, means all clinically vital antibiotics for serious Gram-negative infections are compromised.

A microwave-assisted protocol based on reductive Heck reaction was developed for regio- and stereoselective construction of the 3-benzazepine core.

Enantioselective palladium(0)-catalyzed C–H arylations of cyclopropanes provide efficient access to dihydroquinolones, dihydroisoquinolones and the BMS-791325 indolobenzazepine core.

Secondary 1,3,2-diazaphospholenes have a polarized P-H bond and are emerging as molecular hydrides. Herein, a class of chiral, conformationally restricted methoxy-1,3,2-diazaphospholene catalysts is reported. We demonstrate their catalytic potential in asymmetric 1,4-reductions of α,β-unsaturated carbonyl derivatives, including enones, acyl pyrroles, and amides, which proceeded in enantioselectivities of up to 95.5:4.5 e.r.

An efficient diversity‐oriented procedure for the two‐step synthesis of 3‐benzazepines is described. The CuI‐catalyzed three‐component coupling of an aldehyde, an alkyne and an amine (A3‐coupling) provides the required propargylamines and assures the generation of diversity. The Pd‐catalyzed intramolecular acetylene hydroarylation reaction selectively creates the seven‐membered 3‐benzazepine framework with full control over the ring size and the geometry around the double bond. Microwave irradiation is demonstrated to be highly efficient in promoting both steps.