Design And Study Of FLP Catalysts

Frustrated Lewis Pairs(FLPs),which contain acid/base dual active centers,have been widely used in the activation of small molecules.Various P/B,N/B and other FLPs have been developed.However,the catalytic activation of CO2 using FLPs as catalysts has been rarely reported.Therefore,we would like to develop new FLPs to realize the catalytic activation and utilization of CO2.During the designing of intramolecular N/B FLPs,we found that B(C6F5)3 efficiently catalyzed the reduction of eanmines in the prensece of pinacolborane under mild conditions.Various functionalized secondary amines and aldehydes could provide the tertial amines in good to excellent yields.In addition,β-deuterated tertiary amines were high selectively synthesized through this proctol in the presence of deuterium water.This protocol provides an alternative method to synthesis of various tertiary amiens and β-deuterated tertiary amines.Meanwhile,we have developed an aminopyridine-borane catalytic system,which acts as intramolecular FLPs to catalyze the reductive methylation of indole with CP2.With two types of catalyst conditions(pyridinamine:9-BBN:triethylamine=10%:30%:30%and pyridinamine:BH3-NEt3:triethylamine=10%:30%:30%),indole could selectively produce 3,3’-diindolylmethane and 3-methylindole.In the presence conditions,3-methylindole and 3,3’-diindolylmethane were obtaine in 87%and 71%,respectively.In addition,we also designed new FLPs based on porphyrin molecules.[10,20bis(3,5-di-tert-butylphenyl)-15-phenyl-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)porp hyrin]-nickel,[bis(10,20-bis(3,5-di-tert-butylphenyl)-15-phenylporphyrin-5-yl)amine]-nick el,[diethyl(10,20-bis(3,5-di-tert-butylphenyl)-15-phenylporphyrin-5-yl)phosphonate]-nick el and[(10,20-bis(3,5-di-tert-butylphenyl)-15-phenylporphyrin-5-yl)diphenylphosphine oxide]-nickel have been firstly synthesized.