Theoretical Study on the Mechanism of Cobalt-Catalyzed C-O Silylation and Stannylation.

Organosilicon and organotin compounds have been widely used in many fields, such as organic synthesis, materials science, and biochemistry, because of their unique physical and electronic properties. Recently, two novel compounds containing C-Si or C-Sn bonds have been synthesized. These compounds can be used for late modification of drug-like molecules such as probenecid, duloxetine, and fluoxetine derivatives.

Catalytic asymmetric oxa-Diels-Alder reaction of acroleins with simple alkenes.

The catalytic asymmetric inverse-electron-demand oxa-Diels-Alder (IODA) reaction is a highly effective synthetic method for creating enantioenriched six-membered oxygen-containing heterocycles. Despite significant effort in this area, simple α,β-unsaturated aldehydes/ketones and nonpolarized alkenes are seldom utilized as substrates due to their low reactivity and difficulties in achieving enantiocontrol. This report describes an intermolecular asymmetric IODA reaction between α-bromoacroleins and neutral alkenes that is catalyzed by oxazaborolidinium cation 1f.

Empowering boronic acids as hydroxyl synthons for aryne induced three-component coupling reactions.

Boronic acids have become one of the most prevalent classes of reagents in modern organic synthesis, displaying various reactivity profiles C-B bond cleavage. Herein, we describe the utilization of a readily available boronic acid as an efficient surrogate of hydroxide upon activation fluoride complexation. The hitherto unknown aryne induced ring-opening reaction of cyclic sulfides and three-component coupling of fluoro-azaarenes are developed to exemplify the application value.

Revised Mechanism of C(sp)-C(sp) Reductive Elimination from Ni(II) with the Assistance of a Z-Type Metalloligand.

Reductive elimination is a key step in Ni-catalyzed cross-couplings. Compared with processes that proceed from Ni(III) or Ni(IV) intermediates, C(sp)-C(sp) reductive eliminations from Ni(II) centers are challenging due to the weak oxidizing ability of Ni(II) species. In this report, we present computational evidence that supports a mechanism in which Zn coordination to the nickel center as a Z-type ligand accelerates reductive elimination.