Incorporation of nitrile groups into fine chemicals is of particular interest through C(sp3)–H bonds activation of alkyl nitriles in the synthetic chemistry due to the highly efficient atom economy. However, the direct α-functionalization of alkyl nitriles is usually limited to its enolate chemistry. Here we report an electro-oxidative C(sp3)–H bond functionalization of acetonitrile with aromatic/aliphatic mercaptans for the synthesis of sulfur-containing β-enaminonitrile derivatives. These tetrasubstituted olefin products are stereoselectively synthesized and the stereoselectivity is enhanced in the presence of a phosphine oxide catalyst. With iodide as a redox catalyst, activation of C(sp3)–H bond to produce cyanomethyl radicals proceeds smoothly at a decreased anodic potential, and thus highly chemoselective formation of C–S bonds and enamines is achieved. Importantly, the process is carried out at ambient temperature and can be easily scaled up.

We achieved sulfonated 4H-3,1-benzoxazines under ambient conditions without any metals and external chemical oxidants via electrochemical radical cascade cyclizations.

Thiocyanate compounds are key intermediates in the synthesis of pharmaceuticals and other sulfur-containing organic compounds. Herein, we first report an electrochemical protocol to synthesize vinyl thiocyanates from decarboxylative coupling of cinnamic acids with NH4SCN in aqueous solution. This method provides thiocyanation products with broad functional group tolerance under ambient conditions.

A new method for the synthesis of vinyl trifluoromethyl compounds from α, β-unsaturated carboxylic acids and CF 3 SO 2 Na has been developed. This electrochemical decarboxylative trifluoro-methylation was found to be highly stereo-selective and afforded products in good yields with wide substrate scope under metal-free and external chemical oxidant-free conditions. Results and DiscussionTo start our investigation, p-methoxycinnamic acid (1 a) and CF 3 SO 2 Na (2) were chosen as model substrates. Under constant current at 5 mA and using LiClO 4 as supporting electrolyte in an [a] F.

Fungal metabolites melanoxadin, MR‐93A, melanoxazal, and MR‐93B were synthesized with the key stereogenic centers derived from commercially available chiral building blocks. The optically active synthetic products with well‐defined absolute configurations provided authentic samples for the stereoisomers of these oxazole‐containing natural products and thus allowed for unambiguous assignments of their relative and absolute configurations. The large discrepancies in the optical rotations between the natural and the pure synthetic samples are discussed. Some errors in the previously reported NMR signal assignments are also corrected.