Chinese Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 44(12), P. 3786 - 3786
Published: Jan. 1, 2024
Language: Английский
JACS Au, Journal Year: 2025, Volume and Issue: unknown
Published: Feb. 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.
Language: Английский
Citations
1
Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: unknown
Published: Dec. 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.
Language: Английский
Citations
4
Biotechnology Journal, Journal Year: 2025, Volume and Issue: 20(1)
Published: Jan. 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.
Language: Английский
Citations
0
Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown
Published: March 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.
Language: Английский
Citations
0
Chinese Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: 45(3), P. 996 - 996
Published: Jan. 1, 2025
Language: Английский
Citations
0
Chemical Science, Journal Year: 2025, Volume and Issue: unknown
Published: Jan. 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.
Language: Английский
Citations
0
Journal of Molecular Structure, Journal Year: 2025, Volume and Issue: unknown, P. 142473 - 142473
Published: April 1, 2025
Language: Английский
Citations
0
Nature Communications, Journal Year: 2025, Volume and Issue: 16(1)
Published: May 20, 2025
Cephalotane diterpenoids, featuring unique and complicated carbon skeletons remarkable antitumor activities from the Cephalotaxus genus, have been gaining increasing attention. Herein, we report asymmetric divergent total synthesis of benzenoid cephalotane-type diterpenoids containing identical 6/6/6/5 tetracyclic bridged δ-lactone skeleton with different oxidation states. A cascade C(sp2) C(sp3)-H activation has developed to efficiently prepare characteristic synthetically challenging through a pivotal palladium/NBE-cocatalyzed process. The feature this strategy is construction three C-C bonds (two C(sp2)-C(sp3) one C(sp3)-C(sp3) bond) formation two cycles chiral centers in single step. application method for rapid assembly demonstrated concise cephanolides A-D (1-4) ceforalide B (5) via late-stage modification.
Language: Английский
Citations
0
Chinese Chemical Letters, Journal Year: 2025, Volume and Issue: unknown, P. 111137 - 111137
Published: March 1, 2025
Language: Английский
Citations
0
Organic Letters, Journal Year: 2024, Volume and Issue: unknown
Published: Oct. 21, 2024
The site-selective alkylation of α-aminotropones is effectively realized via gold(I)-catalyzed electrophilic activation allenamides and allenyl ethers, yielding up to 85% in 30 examples. A dedicated combined spectroscopic computational investigation accounts for both chemo- regioselective profiles the protocol. New opportunities chemical space tropone/tropolone derivatives are identified.
Language: Английский
Citations
2