Photoinduced C(sp3)-H chlorination of amides with tetrabutyl ammonium chloride
A new protocol was developed for the site-selective C(sp3)-H chlorination of amides with tetrabutyl ammonium chloride as the chlorinating agent. The reaction features a tandem sequence that involves a (diacetoxyiodo)benzene-mediated and chloride anion-involved N-H chlorination followed by photoinitiated chlorine atom transfer. A wide variety of carboxamides and sulfonamides were chlorinated at the δ-position by using this method.
Zhu, Yanshuo,Yu, Wei
supporting information
p. 10228 - 10232
(2021/12/13)
Lewis Base-Boryl Radicals Enabled the Desulfurizative Reduction and Annulation of Thioamides
A new protocol for radical transformations of thioamides promoted by Lewis base-boryl radicals is reported. The desulfurizative reduction to access organic amines was enabled utilizing 4-dimethylaminopyridine-BH3 as the boryl radical precursor and PhSH as the polarity reversal catalyst. Alternatively, the chain process for unsaturated thioamides was switched to an annulation reaction using N-heterocyclic carbene-BH3 as the boryl radical precursor and sterically bulky Ph3CSH as the catalyst, allowing for the construction of N-heterocyclic and carbocyclic skeletons.