A highly efficient catalytic asymmetric alkynylation of prochiral CH2 groups in tetrahydroisoquinoline was developed using copper catalyzed cross-dehydrogenative-coupling of sp(3) and sp C-H bonds with the assistance of a photocatalyst and visible light.

A reagent-controlled enantioselectivity switch was uncovered in the asymmetric α-fluorination of β-ketocarbonyls by a chiral primary amine catalyst. By a simple swap of fluorination reagents, both enantiomers of the quaternary fluorination adducts could be obtained with good yields and high enantioselectivity. Mechanistic studies disclosed dual H-bonding and electrostatic stereocontrolling mode...

The μ-amino-borane complexes [Rh2 (L(R) )2 (μ-H)(μ-H2 B=NHR')][BAr(F) 4 ] (L(R) =R2 P(CH2 )3 PR2 ; R=Ph, (i) Pr; R'=H, Me) form by addition of H3 B⋅NMeR'H2 to [Rh(L(R) )(η(6) -C6 H5 F)][BAr(F) 4 ]. DFT calculations demonstrate that the amino-borane interacts with the Rh centers through strong Rh-H and Rh-B interactions. Mechanistic investigations show that these dimers can form by a boronium-me...

Molybdenum sulfide (MoS2) is widely recognized for its catalytic activities where the edges of the crystals turn over reactions. Generating sulfur defects on the basal plane of MoS2 can improve its catalytic activity, but generally there is a lack of model system for understanding metal-centered catalysis on the basal planes. Here, we synthesized a new phase of sub-stoichiometric molybdenum sul...

Bond-selective reaction is central to heterogeneous catalysis. In heterogeneous catalysis, selectivity is found to depend on the chemical nature and morphology of the substrate. Here, however, we show a high degree of bond selectivity dependent only on adsorbate bond alignment. The system studied is the electron-induced reaction of meta-diiodobenzene physisorbed on Cu(110). Of the adsorbate's C...

A Cu-diamine complex effectively catalyses tandem C-N bond formation on 2-(2-haloalkenyl)-aryl halide substrates, to deliver a series of N-functionalised indoles. Anilines, amides and carbamates are all effective coupling partners under the developed conditions.

An efficient synthesis of bifurans via dimerization of cyclopropenes has been successfully developed using a copper-promoted cycloisomerization and palladium-catalyzed dimerization cascade. These novel bifuran structures possess interesting optoelectronic properties.

The copper-catalyzed 1,3-dipolar cycloaddition of an azide to a terminal alkyne (CuAAC) is one of the most popular chemical transformations, with applications ranging from material to life sciences. However, despite many mechanistic studies, direct observation of key components of the catalytic cycle is still missing. Initially, mononuclear species were thought to be the active catalysts, but l...

Using a simple copper catalyst, the alkylation of nitroalkanes with α-bromocarbonyls is now possible. This method provides a general, functional group tolerant route to β-nitrocarbonyl compounds, including nitro amides, esters, ketones, and aldehydes. The highly sterically dense, functional group rich products from these reactions can be readily elaborated into a range of complex nitrogen-conta...

By visible-light photoredox catalysis with copper complexes, sulfoximidoyl chlorides add to terminal aryl alkynes give the corresponding (E)-β-chlorovinyl sulfoximines exclusive regio- and stereoselectivities in high yields. Two representative products have been characterized by X-ray crystal structure analysis. Radicals appear be decisive intermediates. As demonstrated two subsequent reactions...