Organolithium compounds, cyclometallated

The organolithium compounds described here have proved to be valuable in the synthesis of a wide range of cyclometallated compounds, many of which are of current interest.7 The precise site of lithiation in these reagents has been determined from investigations of the air-stable products that they form with Me3SiCl and Me3SnCl.8... 

Murahashi, S.-I. Tamba, Y. Yamamura, M. Yoshimura, N. Reactions of cyclometalated Pd complexes with organolithium compounds or Grignard reagents. Selective ortho alkylation and arylation of benzaldehydes, azobenzenes, and tertiary benzylic amines. J. Org. Chem. 1978, 43, 4099-4106. 

The simply prepared cyclometallated complex (24) undergoes coupling reactions with either Grignard reagents or, better, organolithium compounds, in the presence of triphenylphosphine, yielding the o-substituted benzylamines (25) (Scheme 17). The reaction also proceeds smoothly with the corresponding imino- and azo-benzenes. 

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