Iron-Catalyzed Carboamination of Olefins: Synthesis of Amines and Disubstituted β-Amino Acids
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Intermolecular carboamination of olefins with general alkyl groups is an unsolved problem. Diastereoselective carboamination of acyclic olefins represents an additional challenge in intermolecular carboaminations. We have developed a general alkylamination of vinylarenes and the unprecedented diastereoselective anti-carboamination of unsaturated esters, generating amines and unnatural β-amino acids. This alkylamination is enabled by difunctional alkylating reagents and the iron catalyst. Alkyl diacyl peroxides, readily synthesized from aliphatic acids, serve as both alkylating reagents and internal oxidizing agents. A computational study suggests that addition of a nitrile to the carbocation is the diastereoselectivity-determining step, and hyperconjugation is proposed to account for the highly diastereoselective anti-carboamination.Keywords:
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This chapter contains sections titled: Introduction Structural Data on Nitrxle Oxides Nitrile-Oxide-Forming Reactions Nitrile-Oxide-Isocyanate Rearrangement Dimerization and Polymerization of Nitrile Oxides 1,3-Dipolar Cycloaddition Reaction of Nitrile Oxides with Oxygen, Nitrogen and Carbon Nucleophiles Reaction of Nitrile Oxides with Electrophiles Nitrile Sulphides Nitrile Selenides Acknowledgements References
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Although H2S2O8 shows weak oxidizing property at room temperature, it works as a strong oxidizing agent at higher temperature via H2SO5 to H2O2 finally and therefore it had been used only as an oxidizing agent. However, H2O2 oxidizes compounds of lower valency, while it reduces that of higher valency, namely it reduces oxidizing compounds and so H2S2O8, which converted to H2O2 at higher temperature is considered. to react as a reducing agent towards oxidizing com pounds. While H2SO4 was added to heat with KMnO4, MnO2, Ce(SO4)2, CeO2, K2Cr2O7, CrO3, NH4VO3 and V2O5, and then (NH4)2S2O8 was added, they were recognized to be reduced. Therefore, if (NH4)2S2O8 is used as an oxidizing agent, it should be heated after it is added at room temperature, however, in order to use it as a reducing agent, it should be added after it is heated.
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This chapter contains sections titled: Addition Reactions Leading to Cyclic Structures (1,3-Dipolar Gycloadditions)Introduction Preparation of Nitrile Oxides Physical Properties of Nitrile Oxides Reactions of Nitrile Oxides References
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We studied the temperature behavior of the nitrile-stretching band during heating and cooling of polyacrylonitrile (PAN) and the effect of thermal treatment regimes on this behavior. The spectroscopic manifestations of nitrile group intermolecular pairing at temperatures below T g and the polymer thermal expansion at temperatures higher than T g were registered. A comparison of data obtained in different thermal regimes showed that the nitrile group intermolecular attraction influences both the cyclization reaction and its manifestation in the PAN infrared (IR) spectra.
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The 1,3-dipolar cycloaddition of nitrile oxides to 1-cyanoenamines gives 5-aminoisoxazoles regioselectively. Moderate to good yields could be obtained depending on the method used to generate the nitrile oxides. The intermediate isoxazolines could not be isolated.
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Sodium perborate
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Oxidizing sidechain alkyl of benzene ring is one of the most important reactions in the organic synthesis. The methods of oxidizing sidechain alkyl of benzene ring were in recent years, and their advantages and disadvantages were introduced. Then the research direction was put forward.
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