Xiaojing Liu, Jun Yang, Lei Gao, Liyun Zhang, and Xiaoguang Lei
Diels–Alder reaction is one of the most important transformations used in organic synthesis, with the ability to construct two new C–C bonds and up to four chiral centers simultaneously. However, the biggest synthetic challenge in Diels–Alder reaction lies in controlling its regio-, diastereo-, and enantioselectivity.Using Stille cross-coupling and enzymatic Diels–Alder reaction as the key steps, the first chemoenzymatic total synthesis of artonin I is achieved in 30% overall yield over only seven steps. This enzymatic Diels–Alder reaction catalyzed by MaDA is featured with excellent endo- and enantioselectivity and high catalytic efficiency (kcat/KM = 362 ± 54 mm−1 s−1). These successful chemoenzymatic total syntheses of artonin I and dideoxyartonin I demonstrated the remarkable potential of the intermolecular Diels–Alderase MaDA in biocatalysis.
Xiaojing Liu, Jun Yang, Lei Gao, Liyun Zhang, and Xiaoguang Lei* First published: 01 October 2020 https://doi.org/10.1002/biot.202000119
Diels–Alder reaction is one of the most important transformations used in organic synthesis, with the ability to construct two new C–C bonds and up to four chiral centers simultaneously. However, the biggest synthetic challenge in Diels–Alder reaction lies in controlling its regio-, diastereo-, and enantioselectivity.Using Stille cross-coupling and enzymatic Diels–Alder reaction as the key steps, the first chemoenzymatic total synthesis of artonin I is achieved in 30% overall yield over only seven steps. This enzymatic Diels–Alder reaction catalyzed by MaDA is featured with excellent endo- and enantioselectivity and high catalytic efficiency (kcat/KM = 362 ± 54 mm−1 s−1). These successful chemoenzymatic total syntheses of artonin I and dideoxyartonin I demonstrated the remarkable potential of the intermolecular Diels–Alderase MaDA in biocatalysis.