Transition Metal Catalyzed Carbonylation Of Nitro-Compounds

Since the discovery of CO in the 18th century,it has attracted continuous attention from academia and industry.Fischer-Tropsch,Monsanto and Cativa processes have been industrialized to serve people's daily lives.Carbonylation has become an important method for synthesizing carbonyl-containing compounds and extending carbon chains.Introducing nitrogen atoms into compounds generally uses amine compounds as the nitrogen source.Compared with amine compounds,Nitro compounds are more attractive.It has a wide range of sources and abundant species.It is cheaper than it's corresponding amine.And when the nitro compound is reduced in situ during the reaction,it will shorten the reaction by at least one step and improve the reaction efficiency compared with the direct use of amineIn short,there have been many carbonylation directly using amine compounds,but there have a few examples of carbonylation of nitro compounds.Our group has been researching on carbonylation reaction for a long time.Based on previous research,I have studied the carbonylation of nitro compounds.This paper mainly introduces the following work:1.Multi-component carbonylation using inexpensive and readily available substrates to synthesize 2,3-disubstituted-4(3H)-quinazolinones.Under the palladium catalysis,o-iodoaniline,nitroaromatics,and acid anhydrides were used as substrates.By adjusting the reactivity and reaction order between the components,complex 4(3H)-quinazolinone compounds were successfully synthesized in good yields.2.We find that nitroarenes as the amine source and oxidant in this reaaction.Palladium-catalyzed carbonylation of aromatic olefins with nitroaromatics to synthesize a,?-unsaturated amides.A series of substrates were obtained in a moderate to good yield.Through the mechanism,it was verified that nitroarene was used as nitrogen source and oxidant in the system,which is different from general aminocarbonylation.No external reductant or oxidant is needed in this procedure,which is more environmentally friendly and improves the atomic economy of the reaction3.A tunable procedure on palladium-catalyzed carbonylative divergent synthesis of a,b-unsaturated amides and maleimides from symmetrical internal alkynes and nitroarenes has been developed.By using Pd(acac)2/dppp/4-ClBSA/DMF and Pd(TFA)2/DPEphos/PTSA/H20/toluene as the catalytic systems,a range of multi-substituted maleimides and a,b-unsaturated amides were selectively prepared in moderate to good yields with MO(CO)6 as the solid CO source and nitroarene as a cheap and abundant nitrogen source.4.A palladium-catalyzed multicomponent procedure for the selective synthesis of ?-substituted ?,?-unsaturated ketones has been developed.With readily available allenes,arylboronic acids,and nitroarenes as the substrates,the reaction proceeds selectively to the desired ?-substituted enones.Notably,no manipulation of carbon monoxide gas is needed here,and Mo(CO)6 has been applied as a stable solid CO source instead.Additionally,as an oxidative coupling reaction,nitroarenes are used as both the amine source and the oxidant to regenerate the active palladium species.5.A highly selective palladium-catalyzed carbonylative four components procedure for the transformation of allenes,alcohols and nitroarenes has been developed.The desired 2-aminomethyl substituted 3-arylacrylates were produced in good yields with Mo(CO)6 as the solid CO source.Furthermore,nitroarenes have been used as reaction partners and oxidant in this catalytic system.Additionally,further synthetic application of our obtained products has been realized as well and ?-alkylidene ?-lactams were prepared.