Polymeric Pd catalysts for the reduction of acetamidocinnamic acid azlactone and its solvolysis products

Pd complexes have been obtained from linear and cross-linked copolymers ofR,S-, R-, andS-1-(4-vinylphenyl)ethylamine (1) with styrene and divinylbenzene. Reduction of these compounds gave catalysts which were active in the reductive solvolysis of -acetaminocinnamic acid azlactone (2) and hydrogenation of the solvolysis products -acetamidocinnamic acid (ACA), its esters, and its 1-phenylethylamide. The catalysts showed no enantioselective properties in the reductive hydrolysis, but were more active than the catalyst obtained in the absence of the polymer (the monomeric analog). The use of polymeric catalysts has shown that, in reductive aminolysis, the chiral nucleophile plays the dominant part in determining the stereoselectivity of the reaction, rather than the chiral ligand of the catalytic complex. The polymer matrix stabilizes the low-valent state of the palladium in the complex. In the hydrogenation of ACA and its esters, the catalyst on the cross-linked polymer is much more active than its monomeric analog, but showed no enantioselectivity. Hydrogenation of acetamidocinnamic acidR-andS-1-phenylethylamides on a chiral Pd-polymer catalyst occurred with double asymmetric induction.Deceased.N. D. Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, 117913 Moscow. A. V. Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences, 117912 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 10, pp. 2368–2380, October, 1992.     

Asymmetric catalytic synthesis of lysine by hydrogenation of α-nitrocaprolactam

Conclusions The enantioselective hydrogenation of-nitrocaprolactam (I) is effected on a chiral Pd complex, obtainedin situ in the presence of S--phenylethylamine, to give S--aminocaprolactam (II), hydrolysis of which gives S-lysine. The optical yield varies from 1 to 13% according to the solvent and concentration of chiral ligand. On a Pd complex with S-N-isopropyl--phenylethylamine, enantioselective hydrogenation of (I) gives an excess of the S-enantiomer of (II) (2%). On a Pd complex with S-phenylalaninol, hydrogenation of (I) leads to the R configuration of (II) with EE 7.2%.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 7, pp. 1597–1600, July, 1987.     

Effect of pressure on asymmetric synthesis

Russian Chemical Bulletin -     

Asymmetrical synthesis of lysine derivatives

Conclusions The stereoselective aminolysis of the azlactone of DL-diacetyllysine by the action of S--phenylethylamine in t-BuOH leads to an excess of the SS-diastereomer of the -phenylethylamine or diaceyllysine. Crystallization of the mixture of diastereomeric amides gave the optically pure S--phenylethylamide of S-diacetyllysine.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 4, pp. 925–927, April, 1986.