Copper-Catalyzed γ-Selective and Stereospecific Allyl−Aryl Coupling between (Z)-Acyclic and Cyclic Allylic Phosphates and Arylboronates

Abstract

A Cu-catalyzed allyl-aryl coupling reaction between (Z)-acyclic or cyclic allylic phosphates and arylboronates proceeds with excellent gamma-E-selectivity and 1,3-anti chirality transfer, which gives the corresponding coupling products with benzylic and allylic stereogenic centers. The wide availability and easy-to-handle nature of arylboronates, the inexpensiveness of the Cu catalyst system, and the high regio- and stereoselectivities are attractive features of this protocol.

Synthesis of Hindered Anilines: Copper‐Catalyzed Electrophilic Amination of Aryl Boronic Esters

“…With the transmetalation of aryl boronic esters to copper well documented in the literature,16, 21d–e we focused our attention on the electrophilic amination of the putative aryl copper intermediate (Scheme ). A reaction of electrophile 2 with the IMes‐supported copper aryl complex 37 16 resulted in a 73 % yield of aniline 38 , in less than 30 minutes, at room temperature.…”

Copper‐Catalyzed Amination of Arylboronates with N,N‐Dialkylhydroxylamines

“…[16] A second equivalent of boronate 1 then reacts with 7 with the aid of additional LiOtBu to generate a more reactive atetype diarylcuprate 8. There is initial reduction of Cu II into Cu I and ligand exchange with LiOtBu to generate the CuOtBu species 6.…”

Gold(I)‐catalyzed Benzylation of (Hetero)aryl Boronic Acids with (Hetero)benzyl Bromides by the Strategy of a SN2‐type Reaction

“…We proposed two possible reaction patterns of this step. In the first reaction pattern, the naphthyl moiety of Int1 acting as a nucleophile, whose C 1 position was activated by gold catalyst, attacks 2 a through a S N 2 pathway that is similar to the reported mechanism of copper‐catalyzed allylation of arylboronates . The transition state of this process is TS1 with an energy barrier of 24.6 kcal mol −1 .…”