Deprotonative Metalation of Aromatic Compounds by Using an Amino-Based Lithium Cuprate

作者：Tan Tai Nguyen; Marquise Nada; Chevallier Floris; Mongin Florence^*

来源：Chemistry - A European Journal, 2011, 17(37): 10405-10416.

DOI：10.1002/chem.201100990

• bimetallic bases
• copper
• deprotonation
• lithium
• synthesis design

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] (+2LiCl) (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-Bocindole (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.

• 出版日期2011-9