Structure and reaction pathway of TMP-Zincate: amido base or alkyl base?
Structure and reaction pathway of TMP-Zincate: amido base or alkyl base?
复制标题
DOI：
10.1021/ja060489h
复制
发表时间：
2006-06
影响因子：
15
通讯作者：
M. Uchiyama;Yotaro Matsumoto;Daisuke Nobuto;Taniyuki Furuyama;K. Yamaguchi;K. Morokuma
中科院分区：
文献类型：
--
作者：
M. Uchiyama;Yotaro Matsumoto;Daisuke Nobuto;Taniyuki Furuyama;K. Yamaguchi;K. Morokuma
The novel directed ortho metalation (DoM) reagents for functionalized aromatic rings, TMP-Zn-ates (R2Zn(TMP)Li (R = Me, 1; tBu, 2)), have been reported to be synthetically useful for the chemo- and regioselective construction of multi-functionalized aromatic compounds. Here, we present the first comprehensive structural and mechanistic investigation by means of X-ray, NMR, and DFT studies on the DoM reaction employing our original TMP-Zn-ate base. The structures of TMP-Zn-ates in solution and in the solid state were determined. The DFT study strongly suggested that the deprotonation involving the TMP ligand on the TMP-Zn-ate is kinetically more favorable than that involving the alkyl ligand, and this view was supported by monitoring of the 13C NMR spectrum of the reaction mixture.
