A- benzamidocinnamic acid

If we ignore buried species, the only enamine for which we have thermochemical data is a-benzamidocinnamic acid. To estimate its enthalpy of formation, let us assume the following reaction is thermoneutral ... 

Making use of the enthalpy of formation of a-methyldnnamic acid and of solid toluene we predict a value of —436 kJ moP. We recognize that the hydrogenation product of a-benzamidocinnamic acid is iV-benzoylphenylalanine. If we assume that vinyl-N conjugation in enamines is small, then the hydrogenation enthalpy of the compound of interest would equal that of cinnamic acid itself. Equivalently, the reaction... 

Formation of a a-alkylrhodium by insertion of an alkene into a Rh—H bond is a key step in homogeneous asymmetric hydrogenation of alkenes by Rh(I) catalysts. Such intermediates are characterized using multinuclear NMR both in hydrogenation of (Z)-a-acetamidocinnamate by [Rh(Ph2 PCH2 CHj PPhj)] and in the asymmetric hydrogenation of a-benzamidocinnamic acid or its methyl ester by (R,R)-l,2-bis(o-methoxy-phenylphenylphosphino)ethane complexes of Rh(I) . 

Of a number of enamide complexes studied by the present authors, those derived from dipamp proved to be the most rewarding. If the solvate, (53), is reacted with z-a-benzamidocinnamic acid or its methyl ester, then two enamide complexes of similar structure are formed in a ratio of ca 10 1 at room temperature. Since nmr of labeled enamides shows that these have very similar solution structures, they are presumed to be the two diastereomeric complexes (56) and (57), although at this stage the experiment gives no information on their configuration. The DANTE experiment provides the intriguing result that their... 

The preparation of (silyloxy)rhodium complexes of the type [Rh2(fi-OSiR3)2(Ti -COD)2l (R = Me, Ph), which could serve as models of rhodium complexes bound to silica, has been reported238. The synthesis of the water-soluble complex [Rh(Ti -COD)(DPPETS)]+[Cl]" (DPPETS = l,2-bis bis(m-sodiosulfonatophenyl)phosphino ethane) has been reported and its catalytic activity in two-phase hydroformylation reactions investigated. The mechanism of the homogeneous reduction of (Z)-a-acetamido and (Z)-a-benzamidocinnamic acid methyl ester and a-acetamidoacrylic acid methyl ester in an organic-water medium in the presence of catalysts derived from [Rh2(lt-Cl)2(Ti -COD)2] and chiral sulphonated phosphines has been investigated W. ... 

A soln. of methyl p-amino-a-benzamidocinnamate monohydrate in 12 N HGl refluxed 2.5 hrs. p-aminophenylpyruvic acid hydrochloride. Y 86%. Also modified procedure s. A. P. Martinez, Am. Soc. 82, 6050 (1960). 

---