A MOLECULAR RECOGNITION MODEL FOR ENANTIOSELECTIVITY AND AUTOINDUCTION IN CYANOHYDRIN FORMATION CATALYZED BY CYCLO[(S)-HIS-(S)-PHE]

Abstract

A molecular recognition mechanism based on dimeric model for cyclic dipeptide Cyclo[(S)-His-(S)-Phe] (abridged CHP) catalyzed autoinduction is proposed according to the inference of previous experimental findings, which is supported by theoretical calculation with Oniom(B3LYP/3-21G*:AM1) method. The most unstable CHP dimer whose intermolecular hydrogen bonds are immensely lessened by two intramolecular hydrogen bonds is defined as the highest active component (IIa) existing in solid among the three possible dimers (Ia, IIa, and IIb). The carbonyl group of benzaldehyde coordinates to CHP dimer (IIa) by a hydrogen bond with Phe–NαH rather than His–NαH and HCN interacted with the imidazole moiety of His residue to form cyanide ion. In view of the theoretical calculation and experimental results, the structures of the nine-ring complexes derived from interaction between catalytic active dimer CHP(IIa) and cyanohydrins were postulated to explain the enantioselective autoinduction: The structure of no nitrile involved six-ring complex derived from interaction between catalytic active dimer CHP(IIa) and cyanohydrins were postulated to explain the elimination of enantioselective autoinduction.