Amidocuprates for Directed ortho Cupration: Structural Study, Mechanistic Investigation, and Chemical Requirements

摘要

Organocuprate(I) complexes are immensely valuable reagents for both industrial and research chemistry.111 During the past few decades, heteroleptic organocuprates bearing alkynyl, cyano, phenylthio, and phosphi-no groups have secured an important place in organic synthesis. Organo-amidocuprates also represent an important class of heteroleptic cuprates in organic transformations, especially in stereoselective syntheses.In this context, we have recently proposed new uses for amidocuprates, TMP-Cu-ates ([RCu(TMP)(CN)Li]; R = alkyl, phenyl, and TMP; TMP = 2,2,6,6-tetramethylpiperidido), which promote the highly chemoselective, directed ortho cupration of multi-functionalized aromatic compounds under mild conditions. The aryl cuprate intermediate can be employed not only in the trapping of electrophlies, but also in oxidative ligand coupling to form new C—C bonds with alkyl/aryl groups or to introduce a hydroxy group (Scheme 1).