Amines from azides

The synthesis of secondary amines from azides is efficient in terms of chemos-electivity [57] and has found valuable applications in the preparation of diamines [58,59], m-alkylaminoboronic esters [60], and in Diels-Alder-based amination reactions [61]. A convenient general route to open-chain polyamines, which play major roles in cellular differentiation and proliferation, has also been developed using the reductive alkylation of aliphatic aminoazides by (co-halogenoalk-yi)dichloroboranes as a key step [62] (Scheme 21). 

Amines from azides. The oxide reagent is converted in situ into BujSnH by a hydrosilane such as PhSiHj to effect the reduction. 

Amines from azides. Reduction of various azides to amines... 

Amines from azides. The rapid reduction occurs at room temperature using MejSil generated in situ from Me SiCl and Nal in MeCN. 

Amines from azides via acylamines Degradation with loss of 1 C-atom CONs -> NH2... 

Secondary amines from azides. The reaction of alkyldichloroboranes with azides leads to secondary amines directly. This process has been incorporated into a polyamine synthesis. Note that the dichloroboranes can be prepared from organobis (diisopropylamino)boranes. ... 

A later-developed method to obtain amines from azides consists in their reduction with propane-1,3-dithiol,employing ethyldiisopropylamine as a base. The transformations reported proceeded rapidly and resulted in, 2-trans selectivity. Unverzagt described the reduction of the azido heptasaccharide 221 by this dithiol method, to give exclusively the p amine 222. In contrast, reduction of 221 by Raney nickel resulted in both anomers 222 and 223, with p a = 7 3. A corresponding reduction of the azido octasaccharide gave a 52% yield however, a low yield of 35% was observed in the reduction of the thio sugar azide 68 with propane-1,3-dithiol... 

Ethyl cyanoacetate-sodium alcohol Amines from azides... 

Hydrogen sulfide piperidine Amines from azides s. 31, 614... 

Amines from azides under mild conditions... 

Palladium-barium sulfate Amines from azides s. 44, 292... 

Ram, S. R. Chary, K. R Salahuddin, S. Iyengar, D. S. An efficient chemoselective production of amines from azides using AlCl3/NaBH4. Indian J. Chem., Sect. B 2003, 42B, 935-931. 

Na-azide and water added to a soln. of 3 -tosyloxycholestane in dimethylacet-amide, heated 4 hrs. at 90-100°, the dried ethereal soln. of the resulting crude cholestanyl-3a-azide added to a slurry of LiAlH4 in anhydrous ether, and gently refluxed for 3 hrs. -> 3a-aminocholestane. Overall Y 62%.—This is a convenient method for the prepn. of axial amines. F. e. s. A. K. Bose, J. F. Kistner, and L. Farber, J. Org. Ghem. 27, 2925 (1962) amines from azides s. a. F.-X. Jarreau, Qui Khuong-Huu, and R. Goutarel, Bl. 1963, 1861. 

The latest results of the still very productive boron chemistry include a general stereospecific synthesis of sec. amines from azides and di-diloroboranes a simple general synthesis of the didiloroboranes themselves, and the production of alkylboronic acid derivatives from olefins... 

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