Deprotometalation Using Alkali Metal-Amidozincate Complexes

1 Deprotometalation Using Alkali Metal-Amidozincate Complexes 

SCHEME 27.4 Reaction pathways of the DoM reaction of anisole using Me ZnlNMe lIi. Energy changes and bond lengths at the B3LYP/6-31+G and SVP (Zn) level of theory are shown in kcal/mol and A, respectively. 

When the DoM reaction of AlW-diisopropylnaphthamide was examined with EtZn(y/-Et)(//-TMP) Li complex, the resulting crystalline deposit was identified as EtZn[//-Cj HgCON(i-Pr)j2Li-2THP by 

SCHEME 27.5 DoM reaction of VTV-diisopropylnaphthamide using EtZn(/ -Et)() -TMP)Li con )lex to afford EtZn[/ -Cj HjCON(i-Pr)JjLi-2THF. 

Moreover, additional information should be provided herein (i) the stepwise DoM reaction sequence was also indicated with the structurally related complex f-BuZn(//-f-Bu)(//-TMP) Na-TMEDA, having the different countercation (Na) and also additional ligand (TMEDA), by comprehensive DPT calculations [55], and (ii) it was experimentally revealed that the prepared f-Bu2(Ar)ZnLi complex (Ar=2-MeO-CgH ) smoothly deprotonates TMP-H to afford f-Bu(Ar) Zn(TMP)Li, which rephcates the second ligand exchange reaction of the stepwise sequence [56]. Thus, it was concluded that, in general, the stepwise reaction sequence should be the crucial reaction pathway of the DoM reaction with TMP-zincate complexes. 

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