Abstract
Three acylases, including D‐aminoacylase from Escherichia coli, acylase “Amano” from Aspergillus oryzae and immobilized penicillin G acylase from Escherichia coli have been found to possess novel activity to catalyze the Markovnikov addition reaction of N‐heterocycles to vinyl esters. The aza‐Markovnikov addition reactions of 4‐nitroimidazle to vinyl acetate catalyzed by D‐aminoacylase, acylase “Amano” and immobilized penicillin G acylase were up to 1260‐fold, 720‐fold and 320‐fold faster than the respective non‐enzymatic reaction. Some control experiments have been designed to demonstrate the catalytic specificity of acylases. Under the catalysis of these promiscuous acylases, a number of N‐heterocycles, including some pentacyclic N‐heterocycles, pyrimidines and purines, were successfully added to a series of vinyl esters in moderate to excellent yields to prepare N‐heterocycle derivatives. The acylase‐catalyzed Markovnikov addition reaction has provided a new strategy to perform the Markovnikov addition and expanded the application of biocatalysts.