Model Studies on the Enzyme‐Regulated Stereodivergent Cascade Passerini Reaction.

The synthesis of chiral α‐acyloxy carboxamides containing two stereogenic centers continues to be a challenging field of organic chemistry. Herein, we have proposed and proved the feasibility of an enzyme regulated‐cascade reaction, which using the same substrates enables the formation of individual stereoisomers of α‐acyloxy carboxamides with up to 99 % ee. The access to the individual stereoisomeric products has been achieved by a combination of the enzymatic kinetic resolution of racemic vinyl esters, subsequent Passerini reaction, and enzymatic kinetic resolution of formed α‐acyloxy carboxamides. The presented studies are promising in exploratory proof‐of‐concept of enzyme‐controlled stereodivergent cascade to form an important class of chiral compounds for medicinal chemistry. [ABSTRACT FROM AUTHOR]