科研之友
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摘要
Lewis basic substrates, such as vinylphosphines and enamines, can be problematic for transition-metal catalysed hydrofunctionalization reactions due to their propensity to ligate and deactivate transition-metal catalysts as well as form direct Lewis adducts with reaction partners. While exploring rhodium-catalyzed hydroboration of diphenylvinylphosphine with pinacolborane, we found that a high degree of regiocontrol could be achieved without the need to diminish the Lewis basicity of the phosphine by oxidation or prior-protection. At slightly elevated temperature, a high yield of the previously unreported branched regioisomer, 1-pinacolatoborono-1-diphenylphosphinoethane, was achieved with regioselectivity greater than 10:1 using [Rh(COD)Cl](2) as the catalyst and AgOTf as a catalytic additive. Inversion of regioselectivity occurred at low temperature and high yield of the linear regioisomer was observed. Subsequent functionalization of the new branched phosphine-boronic ester and its coordination to rhodium were also investigated.
- 出版日期2018-7-7
