Add time:08/10/2019 Source:sciencedirect.com
The ortho-lithiation of 1,1′-dibromoferrocene is reported for the first time. The reaction is carried out using LDA at low temperature in THF to avoid metathesis. A number of electrophilic quenching reagents have been used, resulting in the formation of a new series of substituted 1,1′-dibromoferrocenes: [(η5-C5H4Br)Fe(η5-C5H3(Br)(R)-1,2)], R=–PPh2, –SCH3, –P(iPr)2, –CHO, –CO2H, –S(O)p-tol. The further derivation of one of these compounds, R=–PPh2, has been carried out, again using a lithiation and quench sequence, to demonstrate the versatility of these product compounds as precursors in their own right. In this manner a range of tri-substituted ferrocenes of the type [(η5-C5H4R)Fe(η5-C5H3(R)PPh2-1,2)], R=–PPh2, –SCH3, –P(iPr)2, –CHO, –CO2H, have been prepared. The ortho-lithiation of bromoferrocene has been similarly achieved and thus this also provides a simple and effective new route to 1,2-disubstituted ferrocenes.
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