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• 622-37-7 Phenyl azide 

Relevant academic research and scientific papers

Synthesis ofN-aryl amines enabled by photocatalytic dehydrogenation

Catalytic dehydrogenation (CD)viavisible-light photoredox catalysis provides an efficient route for the synthesis of aromatic compounds. However, access toN-aryl amines, which are widely utilized synthetic moieties,viavisible-light-induced CD remains a significant challenge, because of the difficulty in controlling the reactivity of amines under photocatalytic conditions. Here, the visible-light-induced photocatalytic synthesis ofN-aryl amines was achieved by the CD of allylic amines. The unusual strategy using C6F5I as an hydrogen-atom acceptor enables the mild and controlled CD of amines bearing various functional groups and activated C-H bonds, suppressing side-reaction of the reactiveN-aryl amine products. Thorough mechanistic studies suggest the involvement of single-electron and hydrogen-atom transfers in a well-defined order to provide a synergistic effect in the control of the reactivity. Notably, the back-electron transfer process prevents the desired product from further reacting under oxidative conditions.

Chiral Synthesis via Organoboranes. 28. Reaction of α-Chiral Organyldichloroboranes with Organyl Azides Providing a Synthesis of Secondary Amines with Exceptionally High Enantiomeric Purities

2-Alkyl-1,3,2-dioxaborinanes R*BO2(CH2)3 of essentially 100percent enantiomeric purity were prepared by the asymmetric hydroboration of readily available prochiral olefins with mono- or diisopinocampheylboranes, followed by removal of the chiral auxiliary (α-pinene).The intermediate R*BO2(CH2)3 reacts readily with lithium aluminum hydride at 0 deg C to give the corresponding lithium monoalkylborohydrides stereospecifically in very good yields and in very high enantiomeric purities.The lithium monoalkylborohydrides, on treatment with hydrogen chloride in dimethyl sulfide, give the corresponding monoalkyldichloroboranes in very high enantiomeric purity.The intermediate monoalkyldichloroboranes react readily with organic azides in 1,2-dichloroethane with evolution of gaseous nitrogen and transfer of the organic group from boron to nitrogen with complete retention of configuration to provide the corresponding secondary amines, either (+)- or (-)-, in very high yields and exceptionally high enantiomeric purities.The procedure was applied to the synthesis of representative optically active amines of high enantiomeric purities (ee or de >99percent), including (2S,2'S)-di-2-butylamine, N--(1S,2R)-trans-2-phenylcyclopentylamine, N(1S,2S)-trans-2-methylcyclohexylamine, and the meso-di-2-butylamine.