An unprecedented N-demethylation of N-methyl amides has been developed by use of N-fluorobenzenesulfonimide as an oxidant with the aid of a copper catalyst. The conversion of amides to carbinolamines involves successive single-electron transfer, hydrogen-atom transfer, and hydrolysis, and is accompanied by formation of N-(phenylsulfonyl)benzenesulfonamide. Carbinolamines spontaneously decompose to N-demethylated amides and formaldehyde, because of their inherent instability.Letter pubs.acs.org/OrgLett
A cyanomethylation of α,β-unsaturated aldehydes with acetonitrile as a nucleophile is disclosed. The reaction is promoted with Cu2O as an inexpensive catalyst. Mild conditions are used, and the reaction completes within a few minutes.
An efficient and convenient protocol for synthesis of dichlorocyanomethyl-functionalized oxindoles through the cascade reactions of dichlorocyanomethyl radical with N-arylacrylamides is reported. The electrophilic dichlorocyanomethyl radical, which is generated from readily available trichloroacetonitrile via a copper-catalyzed singleelectron transfer (SET) process, undergoes radical addition with the electron-deficient C=C bonds of N-arylacrylamides, followed by intramolecular cyclization, to provide dichlorocyanomethyl-functionalized oxindoles. No external oxidant is needed in this transformation.
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