Premium
Deprotonative Metalation of Aromatic Compounds by Using an Amino‐Based Lithium Cuprate
Author(s) -
Nguyen Tan Tai,
Marquise Nada,
Chevallier Floris,
Mongin Florence
Publication year - 2011
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201100990
Subject(s) - aryl , chemistry , electrophile , metalation , thiophene , anisole , lithium (medication) , furan , reagent , cuprate , organic chemistry , medicinal chemistry , combinatorial chemistry , catalysis , materials science , medicine , alkyl , optoelectronics , doping , endocrinology
Deprotonative cupration of aromatic compounds by using amino‐based lithium cuprates was optimized with 2,4‐dimethoxypyrimidine and 2‐methoxypyridine as the substrates and benzoyl chloride as the electrophile. [(tmp) 2 CuLi] (+2 LiCl) (tmp=2,2,6,6‐tetramethylpiperidino) was identified as the best reagent and its use was extended to anisole, 1,4‐dimethoxybenzene, other substituted pyridines, furan, thiophene and derivatives, and N ‐Boc‐indole (Boc= tert ‐butyloxycarbonyl). Of the electrophiles employed to attempt the interception of the generated aryl cuprates, aroyl chlorides, iodomethane, and diphenyl disulfide efficiently reacted. In addition, different oxidative agents were identified to afford symmetrical biaryls. Finally, palladium‐catalyzed coupling with aryl halides was optimized and allowed the synthesis of different aryl derivatives in medium to good yields.