TY - JOUR
T1 - Structure and reaction pathway of TMP-zincate
T2 - Amido base or alkyl base?
AU - Uchiyama, Masanobu
AU - Matsumoto, Yotaro
AU - Nobuto, Daisuke
AU - Furuyama, Taniyuki
AU - Yamaguchi, Kentaro
AU - Morokuma, Keiji
PY - 2006/7/12
Y1 - 2006/7/12
N2 - 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.
AB - 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.
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U2 - 10.1021/ja060489h
DO - 10.1021/ja060489h
M3 - Article
C2 - 16819866
AN - SCOPUS:33745953735
SN - 0002-7863
VL - 128
SP - 8748
EP - 8750
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 27
ER -