Bromine as the ortho-directing group in the aromatic metalation/silylation of substituted bromobenzenes

The one-pot metalation/disilylation of selected bromobenzenes bearing electron-withdrawing substituents p-, m-, o-XC6H4Br (X = F, Cl, I, CN, CF3) using 2 equiv of lithium diisopropylamide (LDA) and 2 equiv of chlorotrimethylsilane (TMSCl) was investigated. The best results of disilylation were obtained for para-substituted bromobenzenes, but the regioselectivity of the reaction is strongly influenced by the ortho-directing power of the substituent. On the contrary, the disilylation of meta-substituted bromobenzenes was not efficient or even failed in some cases and hence monosilylated derivatives were isolated as major or sole products. Diverse reactivity was observed for ortho-substituted bromobenzenes, e.g., 2-bromobenzonitrile and 2-bromochlorobenzene, were converted into corresponding disilylated derivatives in a high and moderate yield, respectively, whereas 1-bromo-2-(trifluoromethyl)benzene underwent only monosilylation.