Synthesis primary amines

Reduction of azides is a classical approach to primary amine synthesis. Treatment of 17 with sodium azide in DMF or in THF/H2O mixtures in the presence of phase transfer catalysts effects a quantitative conversion to the corresponding polymeric azide, 27. Recently the reduction of azides to primary amines via hydrolysis of iminophosphoranes produced by interaction of the azide with triethyl phosphite was reported.30 Application of this technique to the azidomethyl polymer, 27, as shown below, failed to produce a soluble polyamine. 

An efficient primary amine synthesis via iV-diisobutylaluminium imines has been described. A cyanide R CN (R1 = Bu, CsHn, Ph, 2-furyl or 2-thienyl) is treated with diisobutylaluminium hydride and the product is converted into the amine by reaction with an organomagnesium or organolithium compound R2M (R2 = Bu, t-Bu, allyl or benzyl)... 

Chemoselective primary amine synthesis is directly from ketones and ammonia, and is a very challenging project [316], TolBINAP-Ru complex can catalyze the reductive amination of certain ketones to give the corresponding amines in up to 95% e.e. (Eq. 2.39) [317]. 

Auxiliary methods can hold current value when the auxiliary is inexpensive, available in both enantiomeric forms, and, for amine synthesis, can be incorporated with concomitant generation of the new stereogenic a chiral amine center. Reductive amination with chiral ammonia equivalents not only holds this potential but is now a proven and established method that allows chiral primary amine synthesis in two reaction steps (reductive amination and hydrogenolysis) from prochiral ketones. The approach is of interest because of its overall reaction step efficiency. 

Scheme 7.10 Two step chiral primary amine synthesis reductive amination followed by hydrogenolysis.

The Carbanion Chemistry of Tertiary a-Chiral Primary Amine Synthesis.140... 

Although the strategies represented in Table 8.1 are comprehensive, but restricted based on their industrial promise or brevity, they do not represent cohesive general solutions to the problem of a-chiral primary amine synthesis. Instead they offer substrate specific solutions, and their individual limitations will be shortly discussed. Regardless, these methods represent significant advancement in know how regarding the number of reaction steps, yield, and ee, from just 5 to 10 years ago. 

THE CARBANION CHEMISTRY OF TERTIARY a-CHIRAL PRIMARY AMINE SYNTHESIS... 

Compound (I) has a close resemblance to sodimn acet-bromoamide, [CHgCONNaBr], which is an INTERMEDIATE PRODUCT in Hoffman s primary amine synthesis. 

This reaction is related to the Gabriel Primary Amine Synthesis and Sommelet Reaction. 

Other references related to the Gabriel primary amine synthesis are cited in the literature. ... 

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