Amine alkanal imine

Na(BH3CN] (sodium cyanoborohydride) Alcohols, water, DMSO 0 to RT ketone —> alcohol aldehyde —> alcohol alkyl halide —> alkane imine —> amine... 

Generally, the addition of chlonne or bromine to tnfluoroacetonitrile leads to a mixture of partially halogenated imines, amines and azo alkanes [270, 271] In special cases, such as the HgF2-mediated addition of bromine, N,N dihaloper-fluoro-2-alkylamines can be obtained in good yields [272]... 

Aliphatic amines can be readily oxidized by Pd(II) to imines or iminium salts and hydrido complexes. The latter can transfer hydrogen to alkenes, leading to the formation of alkanes as byproducts of the Heck reaction (last example, Scheme 8.18). Such reactions can be avoided by using alkali carbonates as base instead of aliphatic amines [148]. Treatment of stannanes or organoboron derivatives with electron-deficient alkenes under acidic reaction conditions can also lead to formal products of Michael addition instead of the products of a Heck-type reaction [149, 150] (Scheme8.19). 

Difluoroamine reacts with primary and secondary amines to give alkanes (32). With imines, a variety of products are obtained depending on the structure of the imine. The three types of compounds obtained are diazirines (I), a-haloazo compounds (II), and a-fluoroalkylidine-hydrazines (III) (138, 139). The reaction of HNF2 with formaldehyde imines or negatively substituted aromatic imines yields diazirines in fair yield as the principal product, whereas with imines derived from aliphatic aldehydes the reaction gives a mixture of the corresponding diazirine derivative and a-fluoroazo compound. 

Diazo Alkanes, Polynitro. They are prepd by acidifying the appropriate amine with HNO to form compds useful as ezpls. Thus the compd bis(l, l,l-trinitroethyl-2-N-nitro-ethylene-imine)-dinitromethane,... 

Optically active alcohols, amines, and alkanes can be prepared by the metal catalyzed asymmetric hydrosilylation of ketones, imines, and olefins [77,94,95]. Several catalytic systems have been successfully demonstrated, such as the asymmetric silylation of aryl ketones with rhodium and Pybox ligands however, there are no industrial processes that use asymmetric hydrosilylation. The asymmetric hydrosilyation of olefins to alkylsilanes (and the corresponding alcohol) can be accomplished with palladium catalysts that contain chiral monophosphines with high enantioselectivities (up to 96% ee) and reasonably good turnovers (S/C = 1000) [96]. Unfortunately, high enantioselectivities are only limited to the asymmetric hydrosilylation of styrene derivatives [97]. Hydrosilylation of simple terminal olefins with palladium catalysts that contain the monophosphine, MeO-MOP (67), can be obtained with enantioselectivities in the range of 94-97% ee and regioselectivities of the branched to normal of the products of 66/43 to 94/ 6 (Scheme 26) [98.99]. 

In general, aldehydes, ketones, acids, esters, and acid chlorides are all reduced to the corresponding alcohols hy this reagent. Alkyl halides are unreactive towards DIBAL. Amides are reduced to amines, while nitriles afford aldehydes upon hydrolysis of an intermediate imine. Isocyanates are also reduced to the corresponding imines. Nitro compounds are reduced to hydroxy-lamines. Disulfides are reduced to thiols, while sulfides, suhbnes, and sulfonic acids are unreactive in toluene at 0°C. Tosylates are converted quantitatively to the corresponding alkanes. Cyclic imides can be reduced to carbinol lactams. 

Imines undergo addition of one mole of hydrogen in the presence of a catalyst such as palladium, platinum, or nickel to produce secondary amines (Eq. 17.10). This process is analogous to the hydrogenation of alkenes to alkanes and of carbonyl compounds to alcohols. 

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