Understanding the Activation of Air-Stable Ir(COD)(Phen)Cl Precatalyst for C-H Borylation of Aromatics and Heteroaromatics.

A newly developed robust catalyst [Ir(COD)(Phen)Cl] (A) was used for the C-H borylation of three dozen aromatics and heteroaromatics with excellent yield and selectivity. Activation of the catalyst was identified by the use of catalytic amounts of water, alcohols, etc., when B2pin2 was used in noncoordinating solvents, while for THF catalytic use of HBpin was required. The results were on par with the in situ based expensive system [Ir(OMe)(COD)]2/dtbbpy or Me4Phen.

Atroposelective Total Synthesis of the Fourfold ortho-Substituted Naphthyltetrahydroisoquinoline Biaryl O,N-Dimethylhamatine.

A stereoselective total synthesis of O,N-dimethylhamatine, an analogue of an axially chiral naphthylisoquinoline natural biaryl product from tropical Ancistrocladus lianas, is reported. The route features a late-stage atropo-diastereoselective biaryl bond formation. Generation of this especially challenging, sterically hindered tetra-ortho-substituted array was achieved by using Nolan's (IPr*NHC)PdCinCl pre-catalyst under mild Negishi coupling conditions. Discussion is offered regarding the selectivity obtained experimentally and predicted from DFT calculations on the key biaryl coupling step that leads to the desired M-diastereomer.

Nanonickel-catalyzed Suzuki-Miyaura cross-couplings in water.

Nickel nanoparticles, formed in situ and used in combination with micellar catalysis, catalyze Suzuki-Miyaura cross-couplings in water under very mild reaction conditions.

A palladium nanoparticle-nanomicelle combination for the stereoselective semihydrogenation of alkynes in water at room temperature.

The addition of NaBH4 to Pd(OAc)2 in water containing nanomicelles leads to the generation of H2 and Pd nanoparticles. Subsequent reduction of disubstituted alkynes affords Z-alkenes in high yields. These reactions are general, take place in water at ambient temperatures, and offer recycling of the aqueous reaction mixture along with low overall E Factors.

Copper-catalyzed hydrophosphinations of styrenes in water at room temperature.

Copper-catalyzed hydrophosphinations of styrenyl systems in water, at room temperature is herein reported, enabled by our 'designer' surfactant TPGS-750-M. This is an attractive alternative to the more common Pd and Pt catalyzed versions.

On the way towards greener transition-metal-catalyzed processes as quantified by E factors.

Transition-metal-catalyzed carbon-carbon and carbon-heteroatom bond formations are among the most heavily used types of reactions in both academic and industrial settings. As important as these are to the synthetic community, such cross-couplings come with a heavy price to our environment, and sustainability. E Factors are one measure of waste created, and organic solvents, by far, are the main contributors to the high values associated, in particular, with the pharmaceutical and fine-chemical companies which utilize these reactions. An alternative to organic solvents in which cross-couplings are run can be found in the form of micellar catalysis, wherein nanoparticles composed of newly introduced designer surfactants enable the same cross-couplings, albeit in water, with most taking place at room temperature. In the absence of an organic solvent as the reaction medium, organic waste and hence, E Factors, drop dramatically.