Closer insight into the reactivity of TMP-dialkyl zincates in directed ortho-zincation of anisole : experimental evidence of amido basicity and structural elucidation of key reaction intermediates

Clegg, W. and Conway, B. and Hevia, E. and McCall, M.D. and Russo, L. and Mulvey, R.E. (2009) Closer insight into the reactivity of TMP-dialkyl zincates in directed ortho-zincation of anisole : experimental evidence of amido basicity and structural elucidation of key reaction intermediates. Journal of the American Chemical Society, 131 (6). pp. 2375-2384. ISSN 0002-7863 (https://doi.org/10.1021/ja8087168)

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Abstract

The new dialkyl(aryl) lithium zincates [(THF)2Li(C6H4−OMe)MeZnMe] (4), [(TMEDA)Li(C6H4−OMe)MeZnMe] (6), [(THF)3Li(C6H4−OMe)tBuZntBu] (7), and [(PMDETA)Li(C6H4−OMe)tBuZntBu] (8) have been prepared by co-complexation reactions of lithiated anisole with the relevant dialkylzinc compound and the relevant Lewis base. These new heterobimetallic compounds have been characterized in solution using 1H, 13C{H}, and 7Li NMR spectroscopy, and the molecular structures of 6 and 8 have been elucidated by X-ray crystallography. In 6 the distinct metals are connected through the anisole ligand which binds in an ambidentate fashion (through carbon−zinc and oxygen−lithium contacts) and also through one of the methyl groups, to close a [LiOCCZnC] six-membered ring; whereas 8 displays an open structure where anisole connects the two metals (in the same mode as in 6) but with the tert-butyl groups exclusively bonded terminally to zinc. Reactivity studies of zincates 4 and 7 with the amine TMP(H) supply experimental evidence that these heterobimetallic compounds are intermediates in the two-step deprotonation reaction of anisole by TMP−dialkyl zincates and show the relevance of the alkyl groups in the efficiency of TMP−dialkyl zincate bases. In addition, important solvent effects have also been evaluated. When hexane is added to THF solutions of compounds 4 or 7, the homoleptic tetraorganozincate [(THF)2Li2Zn(C6H4−OMe)4] (5) is obtained as the result of a disproportionation process. This lithium-rich zincate has also been spectroscopically and crystallographically characterized.

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