Chinese Journal of Organic Chemistry, Год журнала: 2024, Номер 44(12), С. 3786 - 3786
Опубликована: Янв. 1, 2024
Язык: Английский
JACS Au, Год журнала: 2025, Номер unknown
Опубликована: Фев. 14, 2025
Herein, we present a unified strategy for the total synthesis of benzenoid and troponoid Cephalotaxus diterpenoids, specifically cephanolides A B (benzenoids) harringtonolide cephinoid H (troponoids), in 13 to 19 longest linear steps. This relies on palladium-catalyzed Csp2–Csp3 cross–coupling followed by an intramolecular doubly electron-deficient Diels–Alder reaction establish core skeleton complete benzenoids. late-stage regioselective phenol-to-tropone ring expansion was developed convert benzenoids corresponding congeners. work provides regiocontrolled approach achieving synthetic connectivity between diterpenoids.
Язык: Английский
Процитировано
1
Biotechnology Journal, Год журнала: 2025, Номер 20(1)
Опубликована: Янв. 1, 2025
ABSTRACT Terpenoids are widely distributed in nature and have various applications healthcare products, pharmaceuticals, fragrances. Despite the significant potential that terpenoids possess, traditional production methods, such as plant extraction chemical synthesis, face challenges meeting current market demand. With advancement of synthetic biology metabolic engineering, it becomes feasible to construct efficient microbial cell factories for large‐scale terpenoids. This article primarily centers on heterologous expression Saccharomyces cerevisiae , detailing terpenoid biosynthesis pathways through utilization cellular microcompartments, strategies key P450 enzymes synthesis pathway, regulation optimization host metabolism enhance flux synthesis. Additionally, we analyze propose solutions further refine yeast chassis more effective production.
Язык: Английский
Процитировано
0
Journal of the American Chemical Society, Год журнала: 2025, Номер unknown
Опубликована: Март 10, 2025
The family of Cephalotaxus diterpenoids represents a captivating class natural products that are significant interest from both structural and biological perspectives within our community. Here we wish to report 15-step, enantioselective total synthesis the diterpenoid fortalpinoid Q. Our approach highlights (1) Jacobsen's catalytic Claisen rearrangement enabled single-step formation two vicinal stereogenic centers, including an all-carbon quaternary center; (2) mild, oxoammonium salt (TEMPO+BF4-)-promoted dehydrative Nazarov cyclization swiftly forged crucial cyclopentadiene moiety via unfunctionalized tertiary divinyl carbinol (TDC) substrate; (3) facile aldol-lactonization cascade ultimately resolved last obstacle in synthesis.
Язык: Английский
Процитировано
0
Chinese Chemical Letters, Год журнала: 2025, Номер unknown, С. 111137 - 111137
Опубликована: Март 1, 2025
Язык: Английский
Процитировано
0
Chinese Journal of Organic Chemistry, Год журнала: 2025, Номер 45(3), С. 996 - 996
Опубликована: Янв. 1, 2025
Язык: Английский
Процитировано
0
Chemical Science, Год журнала: 2025, Номер unknown
Опубликована: Янв. 1, 2025
An efficient visible-light-driven method for achieving α-site-selective C–H alkylation of tropones was developed. It applied to transform fortunolide A into cephafortunoids and B, marking the first synthesis C 20 Cephalotaxus troponoids.
Язык: Английский
Процитировано
0
Journal of Molecular Structure, Год журнала: 2025, Номер unknown, С. 142473 - 142473
Опубликована: Апрель 1, 2025
Язык: Английский
Процитировано
0
Journal of the American Chemical Society, Год журнала: 2024, Номер unknown
Опубликована: Дек. 17, 2024
(+)-Mannolide B possesses an intriguing and complex 5/7/5/6/6/6-fused hexacyclic scaffold including two bridged-lactone moieties nine contiguous stereocenters, thus represents a formidable challenge for total synthesis. Herein, the evolution of successful strategy synthesis mannolide is described. The 7/5 ring system 7/5/6/6 tetracyclic carbon skeleton was efficiently constructed by ring-closing metathesis starting from commercially available (−)-methyl jasmonate. Attempts to access 6/6 were unexpectedly challenging. Initially, intramolecular Diels–Alder reaction designed; however, desired cyclization precursor could not be obtained. Furthermore, radical cascade investigated produced only one six-membered with poor stereoselectivity at C5. Finally, successfully generated through Pauson–Khand reaction, followed highly regioselective Büchner–Curtius–Schlotterbeck enabling us achieve first (+)-mannolide in 24 steps.
Язык: Английский
Процитировано
3
Опубликована: Апрель 12, 2024
The diversity of complex molecular structures Cephalotaxus diterpenoids poses great challenges in uncovering the pharmaceutical potential these natural products. As a subfamily diterpenoids, 17-nor-cephalotane possess polycyclic frameworks with seven-membered A ring bearing different oxidation states. On basis novel ynol-diene cyclization developed as rapid access to tropone unit, concise and divergent strategy has been successfully established. Combining bioinspired stereoselective dual hydrogenation, enantioselective total synthesis (+)-3-deoxyfortalpinoid F, (+)-harringtonolide, (−)-fortalpinoids M/N/P, analog (−)-20-deoxycephinoid P have achieved 14-17 linear longest steps starting from commercially available materials.
Язык: Английский
Процитировано
1
Опубликована: Апрель 12, 2024
The diversity of complex molecular structures Cephalotaxus diterpenoids poses great challenges in uncovering the pharmaceutical potential these natural products. As a subfamily diterpenoids, 17-nor-cephalotane possess polycyclic frameworks with seven-membered A ring bearing different oxidation states. On basis novel ynol-diene cyclization developed as rapid access to tropone unit, concise and divergent strategy has been successfully established. Combining bioinspired stereoselective dual hydrogenation, enantioselective total synthesis (+)-3-deoxyfortalpinoid F, (+)-harringtonolide, (−)-fortalpinoids M/N/P, analog (−)-20-deoxycephinoid P have achieved 14-17 linear longest steps starting from commercially available materials.
Язык: Английский
Процитировано
1