Amino compounds ketones

The synthedc ndlity of the Henry reaction is shovm in Scheme 3.1, where fi-nitro alcohols are converted into fi-amino alcohols, amino sugars, ketones and other important compounds. 

Consequently, by choosing proper conditions, especially the ratios of the carbonyl compound to the amino compound, very good yields of the desired amines can be obtained [322, 953]. In catalytic hydrogenations alkylation of amines was also achieved by alcohols under the conditions when they may be dehydrogenated to the carbonyl compounds [803]. The reaction of aldehydes and ketones with ammonia and amines in the presence of hydrogen is carried out on catalysts platinum oxide [957], nickel [803, 958] or Raney nickel [956, 959,960]. Yields range from low (23-35%) to very high (93%). An alternative route is the use of complex borohydrides sodium borohydride [954], lithium cyanoborohydride [955] and sodium cyanoborohydride [103] in aqueous-alcoholic solutions of pH 5-8. 

Weak Medium 300 1 15 Alcohols, phenols, and intermolecular hydroxyl to carbonyl bonding <100° 10 100-300 50 1.2- Diols, a- and most /3-hydroxy ketones o-chloro and oal-koxy phenols 1.3- Diols some /3-hydroxy ketones /3-hydroxy amino compounds /3-hydroxy nitro compounds... 

Secondary amino compounds of the type R2N—H add to aldehyde and ketone carbonyl groups in an acid-catalyzed reaction in much the same way as do RNH2 compounds—with one important difference. The product contains the structural unit C=C—N rather than C—C—N and because there is a carbon-carbon double bond, such a substance is called an enamine (alkene + amine). An example is ... 

Trifluoromethyl ketones can also be synthesized from 1-trifluoromethyl-substituted enol ethers, which are readily prepared from aldehydes via a Wittig reaction (Scheme 9). Similar to Ruppert s procedure (Section 15.1.4.3.4), this method has thus far only been used to prepare trifluoromethyl compounds. The a-amino trifluoromethyl ketones produced in the reaction scheme are much less stable than the corresponding a-amino ketones, which leads to the formation of byproducts (a-hydroxy ketones) during attempts to purify the a-amino trifluoromethyl ketones by chromatography on silica gel. 35 ... 

The synthesis (Scheme 9) begins with the appropriate 1-trifluoromethyl-substituted enol ether 43, where R1 is an amino acid side chain or another appropriate carbon chain. The enol ether undergoes reaction with MCPBA in CH2C12 to give the corresponding epoxy ether 44. The epoxy ether is cleaved by reaction of a wide variety of secondary amines to give the a-amino trifluoromethylated ketone 45. Only a few compounds have been synthesized by this method. 35,36 ... 

High yields and enantiopurity have been realized by a highly diastereoselective MPV reduction of protected a-amino aromatic ketones using catalytic amounts of aluminium isopropoxide. The high anti selectivity resulted from the chelation of the (g) nitrogen anion to the aluminium. In contrast, high syn selectivity was obtained with a-alkoxy ketones and other compounds via Felkin-Ahn control.354... 

Many other compounds have been identified as products of the sugar-amino acid reaction. Amongst these are 2,3-butanedione,195 formaldehyde,196 pyruvaldehyde,20,195, 247, 248 3-hydroxy-2-butanone,248 hydroxy-2-propanone,248 and acetaldehyde.73 Imidazoles,196, 249-251 especially 4(5)-methylimidazole, have also been isolated from the reaction under mild conditions, and could have been formed from a-hydroxy ketones or aldehydes plus amino compounds. Following the early identification247 of pyru-valdehyde as a product of the Maillard reaction, much work was done in an attempt to show that this reactive compound plays a major role in the reaction,249 262 254 but, that this is so is by no means certain.7... 

Phthalimido compounds also photocyclise, e.g. [157] gives [158] (Coyle et al., 1978 Coyle and Newport, 1980 Machida et al., 1977,1980b). Azetidines can be prepared by intramolecular photocyclisation of a-amino methyl ketones (Hesabi et al., 1980). Some Mannich bases have been photocyclised to give a... 

Addition of amino compounds to hexafluoroacetone occurs very readily indeed, but subsequent dehydration to form, for example, oximes or semicarbazones from the corresponding adducts does not normally occur. Special procedures usually have to be employed, the most effective being elimination of amines from adducts to form imines that are derived from the ketone, as illustrated in Figure 8.15. 

Hydrogenation of a mixture of amines and aldehydes or ketones results in the formation of unsymme-trical secondary amines. The hydrogenation of the intermediate aldimine or ketimine can be carried out by heterogeneous catalytic hydrogenation over metal catalysts such as platinum, palladium, nickel or Raney nickel. The overall reaction can be regarded as an alkylation of the amino compounds, and also as a reductive amination of the aldehyde or ketone (Scheme 3). 

Michler s Ketone.—similar di-amino compound in which two amino groups are substituted in benzophenone in the para position in each of the benzene rings yields a tetra-methyl amino product which is known as Michler s ketone. 

Condensation reactions of imidazole C-aldehydes and -ketones with amino compounds, active methylene compounds, and other nucleophiles... 

---