A mild and efficient approach for highly regio- and enantioselective copper-catalyzed hydroboration of 1,1-diaryl substituted alkenes with bis(pinacolato)diboron (B2Pin2) was developed for the first time, providing facile access to a series of valuable β,β-diaryl substituted boronic esters with high enantiomeric purity. Moreover, this approach could also be suitable for hydroboration of α-alkyl styrenes for the synthesis of enantioenriched β,β-arylalkyl substituted boronic esters. Gram-scale reaction, stereospecific derivatizations, and the application of important antimuscarinic drug (R)-tolterodine for concise enantioselective synthesis further highlighted the attractiveness of this new approach.

The copper-catalyzed oxidative amidation of readily available α,β-unsaturated ketones with N-fluorobenzenesulfonimide (NFSI) for the synthesis of biologically active enamides or α-amino substituted unsaturated ketone skeletons has been achieved. These transformations processed via a radical pathway, thus the amidation occurred at the unusual α-position of the α,β-unsaturated ketones, leading to the following effective C(CO)–C(vinyl) or C(vinyl)–H bond cleavage with high selectivity.

AbstractA ligand-controlled regiodivergent and enantioselective copper-catalyzed intermolecular hydroallylation of alkynes with allylic phosphates and hydrosilanes has been achieved for the first time. The chiral bidentate sulfonate-containing N-heterocyclic carbene ligated CuCl complex leads to enantioenriched SN2′-type products, whereas the use of the IMesCuCl catalyst affords SN2-type products. Thus a range of chiral branched and achiral linear 1,4-dienes could be facilely synthesized from readily available alkynes in a regiodivergent manner.

AbstractA ligand-controlled regiodivergent and enantioselective copper-catalyzed intermolecular hydroallylation of alkynes with allylic phosphates and hydrosilanes has been achieved for the first time. The chiral bidentate sulfonate-containing N-heterocyclic carbene ligated CuCl complex leads to enantioenriched SN2′-type products, whereas the use of the IMesCuCl catalyst affords SN2-type products. Thus a range of chiral branched and achiral linear 1,4-dienes could be facilely synthesized from readily available alkynes in a regiodivergent manner.

An efficient Cu-catalyzed synthesis of quinazolines via the C–N bond formation reactions between N–H bonds of amidines and C(sp3)–H bonds adjacent to sulfur or nitrogen atoms in the commonly used solvents, such as DMSO, DMF, DMA, NMP or TMEDA, followed by intramolecular C–C bond formation reactions was developed for the first time.

An efficient Cu-catalyzed synthesis of quinazolines via the C–N bond formation reactions between N–H bonds of amidines and C(sp3)–H bonds adjacent to sulfur or nitrogen atoms in the commonly used solvents, such as DMSO, DMF, DMA, NMP or TMEDA, followed by intramolecular C–C bond formation reactions was developed for the first time.