Studies On Oxidation Reaction And Coupling Reaction Of Alkynes Catalyzed By Metalloporphyrins

Carbon-carbon triple bonds,the functional group of alkyles,which exist extensively in the nature,and the functionalization of carbon-carbon triple bonds are abundant in orgnaic synthesis.The oxidation reaction and coupling reaction of carbon-carbon triple bonds are the important research fields of organic synthesis methodology.The functionalization of carbon-carbon triple bonds mediated by transition-metalloporphyrins was studied in this work.Some new access of the oxidation,and the homo-coupling and cross-coupling of carbon-carbon triple bonds are established,as well as the mechanisms were proposed based on the proof test.We defined the mechanisms of oxidative rearrangement reaction of alkynes reacted with molecular oxygen,as well as terminal alkyne coupling reactions,catalyzed by metalloporphyrin.These findings have an important scientific value and theoretical significance in term of the theories of organic synthesis and porphyrin chemistry.This thesis is divided into five parts as follows:A general review on the development of oxidation reaction and coupling reactions of alkynes,and discuss the research achivemnt and the main fault.At the same time,the oxidation reaction and the coupling reaction catalyzed by metalloporphyrins are reviewed in brief.A series of porphyrins and metalloporphyrins are synthesised,as well as some internal alkynes according to the needs of this topic research.The porphyrins are characted with UV-Vis absorption spectra,mass-spectra,and nuclear magnetic resonance spectroscopy,and the metalloporphyrins are characted with UV-Vis absorption spectrum based on the porphyrins.A new method for the oxidative rearrangement of internal alkynes catalyzed by manganese-(III)porphyrin has been developed,which opens a new access to one-carbon-shorter ketones using molecular oxygen in hexane.In order to find an optimizated reaction conditions,reaction of 1,2-diphenylacetylene was investigated using various metalloporphyrins,solvents,oxidant,and temperatures.Consequently,we decided to set heating 1 mmol alkynes at 150 °C in the presence of 10-6 mol TPPMn Cl in 5 m L n-hexane under 2 MPa of O2 for 4 hours.Most of internal alkynes containing different substituent can sustain this oxidative rearrangement reaction and get the correspondence ketone.To shed some light on the mechanism of this transformation,a series of control experiments were conducted.And the results presented it was an intramolecular synergistic mechanism in the contral experiments.A plausible mechanism was proposed based on the contral experiments and literature reports.A new method of copper porphyrin-catalyzed Glaser-Hay-type couplings of terminal alkynes generating 1,3-diynes is described.Terminal alkynes can be coupled smoothly and features high TON(up to 950)in metalloporphyrin/methanol system without any other addictives.In order to find an optimizated reaction conditions,reaction of phenylacetylene was investigated using various metalloporphyrins,solvents,oxidant,and temperatures.Consequently,we decided to set heating 1 mmol alkynes at 50 °C in the presence of 10-3 mmol T(p-Cl)PPCu in 5 m L methanol under the atmospere of air for 1 hour.Most of terminal alkynes containing different substituent can sustain this homocoupling reaction and get the correspondence 1,3-diynes.To make sure of the mechanism of this transformation,a series of control experiments were conducted.And the results presented it was an a radical process in the contral experiments.A plausible mechanism was proposed based on the contral experiments and literature reports.An effective method of copper porphyrin-catalyzed the hemecoupling of terminal alkynes generating 1,3-diynes is described.Different types of terminal alkynes can be hemecoupled smoothly in metalloporphyrin/methanol system without any other addictives.In order to find an optimizated reaction conditions,reaction of phenylacetylene was investigated using various metalloporphyrins,solvents,oxidant,and temperatures base on the homocoupling reaction.Consequently,we decided to set heating the reaction at 50 °C in the presence of 10-3 mmol T(p-Cl)PPCu in 5 m L methanol with 1?1.2 different substrates under the atmospere of air for 1 hour.A sery of asymmetric 1,3-diynes containing different substituents were got in this hemecoupling reaction with good selectivities.