Adsorption and Performance of Chiral Cinchona Alkaloid Modifiers over Pd/C Catalyst for Enantioselective Hydrogenation of α-Phenylcinnamic Acids

• Published in: Bulletin of the Chemical Society of Japan Vol. 89; no. 10; pp. 1187 - 1191
• Main Authors: Nakatsuji, Makoto, Misaki, Tomonori, Okamoto, Yasuaki, Sugimura, Takashi
• Format: Journal Article
• Language: English
• Published: Tokyo The Chemical Society of Japan 15.10.2016; Chemical Society of Japan
• Subjects: Adsorption; Alkaloids; Enantiomers; Hydrogenation; Metal surfaces; Palladium; Steric hindrance
• ISSN: 0009-2673; 1348-0634
• DOI: 10.1246/bcsj.20160162

The enantioselective hydrogenation reactions of α-phenylcinnamic acid (PCA) and 4,4′-dimethoxy α-phenylcinnamic acid (DMPCA) were carried out over chiral cinchona alkaloid-modified Pd/C. Two sets of the modifiers were employed to get deeper insights into the effects of relative adsorption strength between the modifier and the substrate on the enantioselectivity; cinchonidine (CD)/cinchonine (CN) and quinine (QN)/quinidine (QD). The performances of the two sets of modifiers were compared by systematically varying the modifier concentration over a wide range. It was clearly substantiated that the origin of the low selectivity observed with QN/QD at an ordinary concentration is primarily due to its weak adsorption strength on Pd metal surface, which originates from the steric hindrance of the methoxy substituent at C6. A new modifier, 6-hydroxy CD, was found to exhibit a performance comparable to that of CD, implying that the steric hindrance of the 6-methoxy group of QN/QD is much more influential than the electronic effects.