Selective Catalytic Reaction Of Cyanide And Hydrosilylation With Chiral Ligand Control

Silicone compounds are a kind of important heteroatom or elemental organic compounds,which play an important role in organic chemistry and polymer chemistry.The involvement of organosilicon reagents in selective addition reactions has been an important issue that plays an important role in reactivity in asymmetric reactions or chemical selectivity.Silicone reagents are an important way to build more complex molecules and have important uses in many addition reactions and polymerization reactions.First,we can obtain new Ar-BINMOLs ligands with multiple chiral centers with both C2-axis chirality and sp³-carbon chirality based on the[1,2]-Wittig rearrangement reported previously by the subject group.We further derived Py-BINMOL ligands.The catalytic activity of novel chiral Py-BINMOL ligands in the asymmetric 1,4-conjugated addition reaction of asymmetric TMSCN reagent with?,?-unsaturated ketone was studied.By double activation,the reaction yields moderate to good enantioselectivity and yield.Secondly,for the 1,2 Addition reaction of TMSCF₃ with?,?-unsaturated ketone,a method of direct catalytic trifluoromethylation with Cs₂CO₃ as catalyst and room temperature was designed and developed.The catalytic process was simple and efficient The Compared with the previous literature,the method is separated from the quaternary ammonium salt catalyst system,and the use of fluorine-containing reagents is avoided.The method is simple,efficient and green.The carbonate anions play a role in the induction reaction in the reaction,which has not been reported previously,which provides a new idea and method for further study of the catalytic carbonyl addition reaction.Finally,we based on Py-BINMOL ligand and amide phosphine ligand to expand,and K₂PtCl₄ molecular assembly and coordination,to hydrosilylation reaction as a model to discuss its assembly is successful.We found that when there is no ligand,the hydrosilylation reaction has a good reaction effect and a relatively low chemical selectivity.Py-BINMOL conditions,the platinum catalyst has a lethal effect.Amide phosphine ligand conditions,the reaction showed high reactivity and high chemical selectivity.When the two ligands are used in combination,the activity of the reaction is still high,and the chemical selectivity is further improved,indicating that the two ligands act together to activate.Since the single crystal can not be obtained,the assembly mode and the catalytic mechanism of the double ligand single metal are not clear and need to be further studied.