Amines reaction with alkenes

Other nitrogen compounds, among them hydroxylamine, hydrazines, and amides (15-9), also add to alkenes. Even with amines, basic catalysts are sometimes used, so that RNH or R2N is the actual nucleophile. Tertiary amines (except those that are too bulky) add to Michael-type substrates in a reaction that is catalyzed by acids like HCl or HNO3 to give the corresponding quaternary ammonium salts. " ... 

Benzotriazol-l-yl)methyl]triphenylphosphonium chloride 848 reacts with BunLi and aldehydes to give l-(alken-l-yl)benzotriazoles 849. Addition of bromine to the double bond of derivatives 849 followed by a reaction with amines furnishes amides 850. A variety of primary or secondary amines can be used. This way aldehydes are conveniently homologated and converted to amides with a one-atom longer chain (Scheme 136) <2004ARK(ix)44. 

The conjugate addition of heteronucleophiles to activated alkenes has been used very often in organic synthesis to prepare compounds with heteroatoms [3 to various activating functional groups, e.g. ketones, esters, nitriles, sulfones, sulfoxides and nitro groups. As in the Michael reaction, a catalytic amount of a weak base is usually used in these reactions (with amines as nucleophiles, no additional base is added). 

In the analogous reaction with amines, protonation occurs primarily at the basic amine nitrogen rather than the alkene moiety, forming a nonnucleophilic ammonium salt. 

General aspects of this reactivity,including theoretical studies,have been reviewed. Particular attention has been paid to reactions with amines to get more information on metal-catalyzed hydroamination of alkenes. A recent DFT theoretical study has evaluated the hydroamination process for different metals, concluding that nucleophilic attack of amine is thermodynamically and kinetically favorable for group 10 metals. " ... 

Reaction with Amines and Amides. Reaction of amines with alkenes proceeds most smoothly as an intramolecular version. Amides can be used in the intramolecular reaction to afford various heterocyclic compounds. In the example shown in eq 15, it should be noticed that the Pd species is regenerated by the p-elimination of OH, rather than the /3-hydrogen. For this reason the reaction proceeds catalytically without a Pd° reoxidant. 

Alkylaziridines can be stereospecifically deaminated to alkenes by reaction with m-chioroperbenzoic acid (70AG(E)374). The reaction and work-up are carried out in the dark to avoid isomerization of the cw-alkene, and the mechanism is thought to involve an initial oxidation to an amine oxide followed by a concerted elimination. Aziridine oxides have been generated by treating aziridines with ozone at low temperatures (71JA4082). Two... 

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