A method for base-promoted arylation of arenes and heterocycles by aryl halides and aryl triflates is described. Additionally, in situ electrophilic trapping of ArLi intermediates generated in the reaction of benzyne with deprotonated arenes or heterocycles has been developed, providing rapid and easy access to a wide range of highly functionalized polyaryls. Base-promoted arylation methodology...

A concise and atom-economical Suzuki-Miyaura coupling of trialkyl- and triarylboranes with aryl halides is described. This new protocol represents the first general, practical method that efficiently utilizes peralkyl and peraryl groups of the unactivated trialkyl- and triarylboranes for the Suzuki-Miyaura coupling reaction.

Stabilized AlHCl(2)·(THF)(2) hydroaluminates RC≡CH with exceptional chemo-, regio- and stereoselectivity under efficient ZrCl(2)(η-C(5)Me(5))(2) catalysis (2-5 mol%). The resulting vinyl alanes undergo palladium cross-coupling with a wide range of sp(2) electrophiles (aryl, heteroaryl and vinyl halides/pseudohalides) in good to excellent yields.

Conditions for the Suzuki-Miyaura coupling of lithium triisopropyl borates are reported, as well as a procedure for a one-pot lithiation, borylation, and subsequent Suzuki-Miyaura coupling of various heterocycles with aryl halides. These borate species are much more stable toward protodeboronation than the corresponding boronic acids and can conveniently be stored on benchtop at room temperature.

Unactivated yne-en-ynes reacted with a range of substituted aryl halides in the presence of Pd(OAc)2-PPh3 to afford diazaspiro[4.5]decane with exocyclic double bonds. Three carbon-carbon bonds are formed in this domino reaction, which involves highly regioselective C-C coupling and spiro scaffold steps.

The utilization of perfluoro-tagged palladium nanoparticles immobilized on fluorous silica gel through fluorous-fluorous interactions (Pd(np)-/FSG) or linked to silica gel by covalent bonds (Pd(np)-) in the alkynylation of terminal alkynes with aryl halides under aerobic, copper- and phosphine-free conditions in water, and their recovery and re-utilization, is described.

Organomanganese reagents were prepared by the insertion of magnesium into aryl halides in the presence of MnCl2·2LiCl. These organomanganese reagents smoothly undergo 1,2-addition, acylation, and Pd-catalyzed cross-coupling with various electrophiles. Especially, the oxidative homocoupling of organomanganese reagents was completed in one pot without an additional transition-metal catalyst.

Various functionalized aryl and heteroaryl aluminum reagents were obtained by performing I-Li or Br-Li exchange reactions with the corresponding unsaturated organic halides in the presence of i-Bu2AlCl. By means of an appropriate catalyst, the resulting new aluminum species were directly acylated, allylated or arylated. 1,4-Michael additions to enones have also been achieved.

A new cobalt-catalysed reductive coupling of aryl halides with benzyl chlorides is reported; a variety of diarylmethanes can be prepared in good to excellent yields under mild reaction conditions using CoBr(2) as catalyst and Zn dust; this new cobalt-catalysed coupling represents a practical and interesting alternative to previously known methods for the synthesis diarylmethanes.

Surfactant-free, single-nano-sized copper nanoparticles (Cu NPs) (size: about 2 nm) were prepared by the DMF reduction method. The Cu NPs showed high catalytic activity (with a turnover number (TON) of up to 2.2 × 10(4)) in Ullmann-type cross-coupling of aryl halides with phenols under ligand-free conditions.