Total Synthesis of (−)-Sigillin A: A Polychlorinated and Polyoxygenated Natural Product

Yamaoka, Yousuke; Nakayama, Tadanobu; Kawai, Shigeyuki; Takasu, Kiyosei

doi:10.1021/acs.orglett.0c02930

Chemoenzymatic Synthesis of the Cyclopiane Family of Diterpenoid Natural Products

Wang,

Zou,

Wang

et al. 2024

Angewandte Chemie

0

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A three‐stage chemoenzymatic synthesis of the cyclopiane family and related diterpenes is reported. Deoxyconidiogenol with a 6/5/5/5‐fused tetracyclic cyclopiane skeleton was first produced by an engineered E. coli host harboring the corresponding terpene cyclase PchDS. Ten cyclopiane diterpenes were synthesized by late‐stage functionalization of rings A, B and D of the cyclopiane skeleton through direct redox operations, directed C‐H activation, and enzymatic hydroxylation, respectively. Skeletal diversification was achieved by taking advantage of the selective 1,2‐alkyl migration of a cyclopiane cation generated chemically or enzymatically. Three cyclopiane‐related skeletons, including the spiro 5/5/5/5‐tetracyclic skeleton of spiroviolene, the angular 5/6/5/5‐fused ring system of phomopsene, and the new linear 5/6/5/5‐fused tetracyclic ring system of amycolatene, were produced either by chemical skeletal transformation from the cyclopiane skeleton, or by terpene cyclases discovered by genome mining.

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Chemoenzymatic Synthesis of the Cyclopiane Family of Diterpenoid Natural Products

Wang,

Zou,

Wang

et al. 2024

Angew Chem Int Ed

0

View full text Add to dashboard Cite

A three‐stage chemoenzymatic synthesis of the cyclopiane family and related diterpenes is reported. Deoxyconidiogenol with a 6/5/5/5‐fused tetracyclic cyclopiane skeleton was first produced by an engineered E. coli host harboring the corresponding terpene cyclase PchDS. Ten cyclopiane diterpenes were synthesized by late‐stage functionalization of rings A, B and D of the cyclopiane skeleton through direct redox operations, directed C‐H activation, and enzymatic hydroxylation, respectively. Skeletal diversification was achieved by taking advantage of the selective 1,2‐alkyl migration of a cyclopiane cation generated chemically or enzymatically. Three cyclopiane‐related skeletons, including the spiro 5/5/5/5‐tetracyclic skeleton of spiroviolene, the angular 5/6/5/5‐fused ring system of phomopsene, and the new linear 5/6/5/5‐fused tetracyclic ring system of amycolatene, were produced either by chemical skeletal transformation from the cyclopiane skeleton, or by terpene cyclases discovered by genome mining.

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Naturally Occurring Organohalogen Compounds—A Comprehensive Review

Gribble

¹

2023

Progress in the Chemistry of Organic Natural Products

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Total Synthesis of (−)-Sigillin A: A Polychlorinated and Polyoxygenated Natural Product

Cited by 10 publications

References 31 publications

Chemoenzymatic Synthesis of the Cyclopiane Family of Diterpenoid Natural Products

Chemoenzymatic Synthesis of the Cyclopiane Family of Diterpenoid Natural Products

Chemoenzymatic Synthesis of the Cyclopiane Family of Diterpenoid Natural Products

Naturally Occurring Organohalogen Compounds—A Comprehensive Review

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