Boranes, reaction with chloramine

Organoboranes react with a mixture of aqueous NH3 and NaOCl to produce primary amines. It is likely that the actual reagent is chloramine NH2CI. Chloramine itself,hydroxylamine-O-sulfonic acid in diglyme, and trimethyl-silyl azide " also give the reaction. Since the boranes can be prepared by the hydroboration of alkenes (15-16), this is an indirect method for the addition of NH3 to a double bond with anti-Markovnikov orientation. Secondary amines can be prepared by the treatment of alkyl- or aryldichloroboranes or dialkylchlorobor-anes with alkyl or aryl azides. 

Several papers have appeared describing the synthesis of alkyl halides from organoboranes. Alkyl chlorides are obtained by the reaction of trialkylboranes with dichloramine-T, and in somewhat lower yield with iV,N-dichlorourethane/ whereas alkyl bromides are produced in excellent yield when the boranes derived from terminal alkenes and dicyclohexylborane are treated with either Bt2 or BrCl. Alkyl iodides are obtained from the same boranes by the use of ICl-NaQAc " or iodide ion-chloramine-T/ and this latter method has been applied to the radioiodination of olefins (with Vinyl iodides result from... 

Amines can be obtained under mild conditions from amides by reduction with borane and also from ethylene derivatives with borane and hydroxylamine-O-sulfonic acid or chloramine A modified Schmidt reaction gives good yields of N-subst. trifluoro-acetamides... 

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