Azides reaction with organoboranes from

The reaction of trialkylboranes with iV-chloroalkylamines can be used to synthesize a wide variety of functionally substituted dialkylamines in good yields [66,67], and it complements the synthesis of secondary amines via the reaction of trialkylboranes with organic azides. The reaction is analogous to the reaction of chloramine with organoboranes, and presumably occurs via an anionotropic migration of an alkyl group from boron to nitrogen (Scheme 24). 

A more convenient procedure for the synthesis of (113) from (5) was later elaborated <9UOM(4l2)l>. It is based on the intramolecular version of the reaction of organoboranes with organic azides. The THF complex of 1-boraadamantane (5a) is treated with iodine in the presence of an excess of sodium azide. The iodine atom in the intermediately formed borabicycle (118) undergoes an easy nucleophilic substitution by azide ions. The subsequent anionotropic rearrangement in the borabicyclic azide (119) leads (after the oxidation of the reaction mixture) to aminoalcohol (120), which is smoothly converted to 1-azaadamantane (113). The yield of (113) in this synthesis is 40-45% based on (5a), or 20-22% based on triallylborane (Scheme 44). 

Amines from boranes. A sequential reaction of RBH with BClj and an organic azide leads to the amine with retention of configuration. The following equation illustrates a stereoselective approach to cycloalkylamines on the basis of organoborane... 

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