Carbocyanation of trisubstituted olefins via Cu-catalyzed atom transfer radical addition

Free‐Radical Carbocyanation of Olefins

“…[4] Moreover,t he small size of the CN substituent should allow the elaboration of acyclic systems bearing quaternary centers with an itrile function, ready for further transformation. [7] Recently,I noue et al [8] disclosed an interesting intramolecular cyanide-transfer process during the addition of Cl 3 CCN to an olefin,c atalyzed by ac opper complex. [7] Recently,I noue et al [8] disclosed an interesting intramolecular cyanide-transfer process during the addition of Cl 3 CCN to an olefin,c atalyzed by ac opper complex.…”

“…1,2‐Cyanocarbofunctionalization of alkenes has thus been limited to copper‐catalyzed cyanotrifluoromethylation . Recently, Inoue et al . disclosed an interesting intramolecular cyanide‐transfer process during the addition of Cl 3 CCN to an olefin, catalyzed by a copper complex.…”

Recent Developments in the Polychloroalkylation by Use of Simple Alkyl Chlorides

“…Subsequently, Inoue and co‐workers reported the carbocyanation of trisubstituted olefins, using chlorinated cyanides to introduce chloroalkyl and cyano by C−CN bond cleavage (Scheme 11). [13] This strategy obtains the target products in the presence of Cu(MeCN) 4 PF 6 by 1,3‐transfer of CN. The downside is that the reaction substrates is limited to trisubstituted olefins.…”

“…Recently, with the development of radical chemistry, simple alkyl chlorides (such as dichloromethane, chloroform etc.) have been used as effective precursors to introduce the polychlorinated groups through the coupling with alkanes, [4–7] addition of olefins [9–26] and cyclizations [27–36] . Among them, due to the high reactivity of polychlorinated radical intermediates, the radical‐mediated polychloroalkylation groups have been considered to be an indispensable tool for the synthesis of complex polychlorinated compounds.…”

“…In the past few decades, transition‐metal‐catalyzed (Ru, Rh, Cu, Nb, etc. ), [4,11–17] photoredox catalyzed, [5–6,10,14] and oxidative radical functionalization reactions play an important role in the synthesis of polychlorinated compounds. This review focuses on recent impressive progress in polychloromethylation or polychloroalkylation, highlighting the radical process, initiated by simple alkyl chlorides.…”