Synthesis of Di/Triarylmethanes via Pd-Catalyzed Coupling of Benzylic Phosphates with Arylsilanes

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  Diarylmethanes are regarded as an important class of compounds both in pharmaceutical chemistry and supramolecular structures.Recently,great efforts have been made to develop the transition-metal-catalyzed synthesis of diarylmethanes involving the Pd-catalyzed coupling of benzyl halides or aryl halides with organoboron,1a organotin1b or organozinc.1c Several Cu(Ⅰ)-catalyzed cross-coupling reactions between Grignard reagents and alkyl or benzyl halides2 have also been reported.However,to the best of our knoeledge,no benzylic phosphates,which are readily obtained from corresponding alcohols and are highly stable,have been involved in Hiyama cross-coupling to prepare diarymethanes.Our ongoing interest in phosphate reactivity has led us to explore the possibility of the formation of various unsymmetrical diarylmethanes from the reaction of benzyl phosphates with aryltrialkoxysilane using Pd as a catalyst.As shown in Scheme 1,we have developed the Hiyama-type cross-coupling reactions of benzylic phosphates with arylsilane.This is the frist example that benzylic phosphates function as electrophilic substrates in Pd-catalyzed Hiyama-type crosscoupling reactions.The reaction can tolerate either electron-donating or electronwithdrawing functional groups.
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