Palladium-Catalyzed, Site-Selective Direct Allylation of Aryl C-H Bonds by Silver-Mediated C-H Activation: A Synthetic and Mechanistic Investigation.

ABSTRACT: We describe a method for the site-selective construction of a C(aryl)-C(sp³) bond by the palladium-catalyzed direct allylation of arenes with allylic pivalates in the presence of AgOPiv to afford the linear (E)-allylated arene with excellent regioselectivity; this reaction occurs with arenes that have not undergone site-selective and stereoselective direct allylation previously, such as monofluorobenzenes and non-fluorinated arenes. Mechanistic studies indicate that AgOPiv ligated by a phosphine reacts with the arene to form an arylsilver(I) species, presumably through a concerted metalation-deprotonation pathway. The activated aryl moiety is then transferred to an allylpalladium(II) intermediate formed by oxidative addition of the allylic pivalate to the Pd(0) complex. Subseque

SUBMITTER: Lee SY 

PROVIDER: S-EPMC5161498 | biostudies-literature | 2016 Nov

REPOSITORIES: biostudies-literature