A copper-catalyzed activation of C(sp)-H bonds of DMF at room temperature was developed, which results in methyl transfer to aromatic amines for efficient synthesis of exceedingly valuable α-amino nitriles. This process features excellent functional group tolerance, a broad substrate scope, and high activity under ambient conditions.
An efficient hydrogen bonding-guided ring-closing metathesis (RCM) reaction of sterically demanding homoallyl 2-(hydroxymethyl)acrylates catalyzed by the Hoveyda-Grubbs 2nd generation catalyst was developed and the reaction mechanism was explored. Adding a substituent to the hydroxymethyl group in this scaffold resulted in a class of challenging RCM substrates, although usable yields could be obtained. However, substrates bearing a 1-oxygenated alkyl group on the homoallylic carbon gave excellent RCM yields, providing a practical solution. Experimental and computational evidence indicated an unusual directing effect of OHCl hydrogen bonding between the substrate and Ru catalyst, which guides Ru to interact with the electron-deficient, more hindered acrylic C[double bond, length as m-dash]C bond and thus triggers the RCM process.
A copper-catalyzed functionalization of inert cyclic ethers was developed to provide α-aminonitriles via a cascade oxidation/amination/ring-opening/cyanation reaction. A series of highly versatile α-aminonitriles were obtained from primary or secondary anilines, and heterocyclic and aliphatic amines with high yields. This process features excellent functional group tolerance, a broad substrate scope, and high activity under ambient conditions.
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