2021 journal article

Deciphering Pyrrolidine and Olefin Formation Mechanism in Kainic Acid Biosynthesis

ACS CATALYSIS, 11(1), 278–282.

By: T. Chen n, S. Xue*, W. Tsai*, T. Chien*, Y. Guo* & W. Chang n

co-author countries: Taiwan, Province of China 🇹🇼 United States of America 🇺🇸
author keywords: metalloenzyme; C-H activation; cyclization; desaturation; enzyme mechanism
Source: Web Of Science
Added: February 15, 2021

Metalloenzyme-catalyzed cyclization involving C–H bond activation is a powerful strategy to construct molecular complexity found in natural product biosynthesis. In the isodomoic acid and kainic acid biosynthetic pathways, mononuclear non-heme iron enzymes catalyze cyclization along with desaturation reactions that install the pyrrolidine and the olefin. Using complementary approaches, a plausible reaction pathway of kainic acid formation is established. Following H atom abstraction by an Fe(IV)-oxo species, the resulting radical interacts with the N-prenyl group to promote pyrrolidine installation. The reaction then undergoes a carbocation-triggered desaturation to construct kainic acid.