Themed collection New advances in catalytic C–C bond formation via late transition metals

The demonstration of a general method for cross-coupling of secondary allylic boronic esters was achieved for the first time under the same Pd-catalyzed conditions previously used for the coupling of benzylic substrates. Unlike allyl silanes, the regioselectivity of the arylation depends on the sterics and electronics of the allylic and vinylic substituents.

Simple variation of phosphine structure allows selective access to alkylative couplings or reductive cycloadditions.

Palladium-catalyzed cross-coupling reactions between 2-(but-3-enyl)phenols and aryl or alkenyl bromides provide straightforward access to substituted chroman derivatives.

Systematic changes, first to the catalyst scaffold and then to the ligating groups, are successfully used to fine tune supramolecular catalyst structures.

Angular tricyclic compounds with a variety of ring-sizes were produced by ring-rearrangement metathesis, sometimes with a high degree of selectivity.

A protocol based on a Pd(OAc)₂/SPhos catalyst system for the Suzuki-Miyaura coupling of heteroaryl boronic acids and vinyl chlorides that minimizes protodeboronation is described.

Regioselective C–H bond arylation and alkylation of acridines using organozinc reagents are described.

A concise synthesis of fused 1,2,3-triazoles is described, featuring a palladium-catalyzed intramolecular Heck or direct arylation reaction.

Decarboxylative coupling of benzylic and heterobenzylic esters results in either benzylation or arylation of nitrile-stabilized anions.

An efficient method to form unsymmetrical diaryl ketones via Fukuyama cross-coupling reactions with low loadings of Pd(dba)₂ has been developed.

A mild Rh-catalyzed carbonylative coupling of benzamides to form phthalimides has been developed.

The use of sterically different ligands in the synthesis of pyridines from oximes and alkynes allows for complementary selectivities to be achieved.

Diazafluorene-derived ligands enable regiocontrolled Pd-catalyzed oxidative coupling of indoles and benzene to proceed with O₂ as the oxidant.

Catalytic addition of silylacetylenes to α,β-unsaturated ketones proceeded in the presence of a cobalt complex coordinated with a bisphosphine ligand to give high yields of β-alkynylketones.

Methallyl chloride serves as an efficient allyl donor in highly enantioselective Grignard Nozaki–Hiyama methallylations from the alcohol or aldehyde oxidation level via iridium catalyzed transfer hydrogenation. Under identical conditions, methallyl acetate does not react efficiently.

An atom-economical, purification free method for the synthesis of tricyclic sultams has been developed utilizing a facilitated ring-opening metathesis polymerization (ROMP) protocol.

In the presence of gold(I)–phosphine catalysts, alkenyl- and arylsilanes undergo intramolecular cyclisation reactions onto appendant alkyne moieties to afford 1-silaindene derivatives. The reaction pathways vary depending on the substituent on silicon.

trans-6-Aryl-4-keto-2-pyranyl-diazoacetoacetates undergo the [1,2]-Stevens rearrangement in a controllable conformation-dependent process.

Aryl chlorides are useful substrates for the palladium-catalyzed N-arylation of a sulfoximine when RuPhos is used as a ligand.

2-Alkylindoles are prepared regiospecifically in a gold-catalyzed bimolecular process under exceedingly mild reaction conditions.

Subtle differences in borane structure strongly influence the efficiency of catalytic asymmetric hydroboration with β,γ-unsaturated Weinreb amide substrates.

The air and moisture stable Pd complex [t-BuPhebox-Me₂]PdBr is capable of efficiently promoting α-monoarylation of ketones with numerous aryl bromides in 1 h at 70 °C with 82–99% yields.

Tandem Au(III)-catalyzed heterocyclization/Nazarov cyclizations leading to substituted carbocycle fused furans are described. An interesting dichotomy of reaction pathways as a function of solvent, confirmed by the isolation and trapping of reaction intermediates, provided a basis for computational studies that supported the experimental findings.

A novel Pd-catalyzed decarboxylative cross-coupling of oxamic acids with potassium phenyltrifluoroborates has been realized under mild reaction conditions.

A Pd(0)/Au(I) redox-driven palladium catalyzed homo-coupling of gold–aryl complexes illustrates potential redox incompatibilities of both metals for the development of Pd/Au dual catalysis.

A new synthesis of an inhibitor of botulinum neurotoxin is reported which involves the formal activation of three C–H bonds.

An efficient protocol is described for the desymmetrisation of a prochiral complex by catalytic desymmetrisation via an asymmetric Suzuki–Miyaura coupling reaction, using a bulky chiral palladium catalyst.

The codimerization of acrylates and alkynes to produce 1,3-dienes is demonstrated using a nickel catalyst in association with 2-aminopyridine.

P,N,O-chelate nickel complexes efficiently catalyse the cross-coupling reaction of arylzinc reagents with aryl chlorides at room temperature with low catalyst loading.

Gold(I)-catalysed reaction between cyclopropenes and furans produces functionalised conjugated trienes.

An unprecedented NH₂-directed Pd(II)-catalytic carbonylation of quaternary N-unprotected arylethylamines to yield selectively 6-membered benzolactams has been developed.

A general protocol for the synthesis of 1-acetoxy-1,3-dienes from alkynes and alkenes by an acetoxypalladation/Heck cross-coupling/β-H elimination tandem process is described.

Nickel-catalysed cross-coupling reactions of aryl(trialkyl)silanes with aryl chlorides and tosylates are described.