Amines carbonyl compounds, Amino nitriles

Amino acids, Amino alcohols, Amino carbonyl compounds, Amino nitriles, Enamines, Homoallylic amines)... 

This methodology is also an important and potentially valuable method for C—N bond formation using the amination of carbon nucleophiles with electrophilic nitrogen transfer reagents (Scheme 1) Amination of ordinary carbanions and a-carbanion derived from carbonyl compounds and nitriles provides an important method for the synthesis of amines and a-amino carbonyl compounds and nitriles", respectively. For this purpose, a number of electrophilic amination reagents, which are synthetic equivalents of the R2N+ synthon, have been developed and the synthetic potential of electrophilic amination of carbon nucleophiles has been studied in detail . ... 

The condensation of activated thiols onto adjacent nitriles is a common method for the preparation of amine-substituted thiophenes. A three component condensation was utilized to prepare a-aminothiophene 11 <00TL1597>. An alternate method for preparing amino-substituted thiophenes involved the treatment of ketene S,JV-acetal 12 with an activated carbonyl compound 13 which gave thiophene 14 <00JOC3690>. This type of reaction has also been utilized to prepare building blocks for the synthesis of fused thiophenes <00JHC363>. 

The amino acid synthesis from Strecker has been known since 1850 [25]. Stereoselective versions of this synthesis start with chiral amines, which are condensed with carbonyl compounds to form imines. Addition of hydrogen cyanide and subsequent hydrolysis of the amino nitriles yields the amino acids. When ketones are used for the condensation, a-alkylated amino acids are obtained in high yields and optical purities... 

Primary amines are oxidized to azo, azoxy, nitroso, or nitro compounds, depending on the oxidants used. Most of the examples include aromatic amines, because aliphatic amines that have hydrogens on the carbons carrying the amino groups may undergo dehydrogenations to carbonyl compounds, imines, and nitriles (see equations 508-514). 

Strecker reaction The condensation of carbonyl compounds with amines and nitriles to afford a-amino nitriles. 446... 

Most of the elementary reactions in the classic MCRs are equilibrium processes. Therefore, thermodynamic factors can significantly impact the reaction pathways in addition to the reaction kinetics. A classic example is the Strecker synthesis of a-amino nitrile 9 from aldehydes, amines, and cyanide (Scheme 15.5). The key step in this reaction is the nucleophilic addition of cyanide to the in situ formed iminium. However, condensation of a carbonyl compound with an amine leading to iminium is an equilibrium process, especially under aqueous conditions. Therefore, the desired addition reaction is in competition with direct addition of cyanide to the aldehyde, leading to cyanohydrin 10. However, since the formation of both 9 and 10 were reversible, only the more stable adduct 9 was produced at the expense of cyanohydrin 10 under thermodynamically controlled conditions. 

Route I leads via the retrosynthetic operations a and b to the or-acylamino carbonyl system 2. This suggests NH3 or a primary amine as starting materials. According to route II, addition of H2O (c) leads to intermediate 1 which can be further dissected in line with the usual retroanalytical scheme. Route d points to an or-halo- or a-hydroxycarbonyl compound and amidine, whereas route e suggests an a-amino ketone and acid amide or nitrile as starting materials. 

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