Structure-Unit-Based Total Synthesis of (-)-Sinulochmodin C.

Autor: Zhang YP; Key Laboratory of Medicinal Chemistry for Natural Resource, Ministry of Education, Yunnan Provincial Center for Research and Development of Natural Products, Yunnan Characteristic Plant Extraction Laboratory, School of Pharmacy, Yunnan University, Kunming, 650091, P. R. China., Du S; Key Laboratory of Medicinal Chemistry for Natural Resource, Ministry of Education, Yunnan Provincial Center for Research and Development of Natural Products, Yunnan Characteristic Plant Extraction Laboratory, School of Pharmacy, Yunnan University, Kunming, 650091, P. R. China., Ma Y; Key Laboratory of Medicinal Chemistry for Natural Resource, Ministry of Education, Yunnan Provincial Center for Research and Development of Natural Products, Yunnan Characteristic Plant Extraction Laboratory, School of Pharmacy, Yunnan University, Kunming, 650091, P. R. China., Zhan W; Key Laboratory of Medicinal Chemistry for Natural Resource, Ministry of Education, Yunnan Provincial Center for Research and Development of Natural Products, Yunnan Characteristic Plant Extraction Laboratory, School of Pharmacy, Yunnan University, Kunming, 650091, P. R. China., Chen W; Key Laboratory of Medicinal Chemistry for Natural Resource, Ministry of Education, Yunnan Provincial Center for Research and Development of Natural Products, Yunnan Characteristic Plant Extraction Laboratory, School of Pharmacy, Yunnan University, Kunming, 650091, P. R. China., Yang X; Key Laboratory of Medicinal Chemistry for Natural Resource, Ministry of Education, Yunnan Provincial Center for Research and Development of Natural Products, Yunnan Characteristic Plant Extraction Laboratory, School of Pharmacy, Yunnan University, Kunming, 650091, P. R. China., Zhang H; Key Laboratory of Medicinal Chemistry for Natural Resource, Ministry of Education, Yunnan Provincial Center for Research and Development of Natural Products, Yunnan Characteristic Plant Extraction Laboratory, School of Pharmacy, Yunnan University, Kunming, 650091, P. R. China.
Jazyk: angličtina
Zdroj: Angewandte Chemie (International ed. in English) [Angew Chem Int Ed Engl] 2024 Jan 08; Vol. 63 (2), pp. e202315481. Date of Electronic Publication: 2023 Dec 08.
DOI: 10.1002/anie.202315481
Abstrakt: Herein we report a structure-unit-based asymmetric total synthesis of sinulochmodin C, a norcembranoid diterpenoid bearing a transannular strained ether bridge β-keto tetrahydrofuran moiety. Our synthetic route features an intramolecular double Michael addition to construct stereospecifically the [7,6,5,5] tetracyclic skeleton, a vinylogous hydroxylation/oxidation procedure or a stereospecific epoxide opening/oxidation sequence to establish the γ-keto enone intermediate, a Lewis acid/Brønsted acid mediated transannular oxa-Michael addition to fuse the β-keto tetrahydrofuran moiety, a Mukaiyama hydration/Pd-C hydrogenation to reverse the C1-configuration of the isopropenyl unit, and a bioinspired transformation of sinulochmodin C into scabrolide A.
(© 2023 Wiley-VCH GmbH.)
Databáze: MEDLINE
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