Divergent Synthesis of 17‐nor‐Cephalotane Diterpenoids through Developed Ynol‐diene Cyclization DOI
Zezhong Sun,

Xin Shu,

Fuli Ma

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(39)

Published: July 9, 2024

Abstract On the basis of a novel ynol‐diene cyclization developed as rapid access to tropone unit, first divergent strategy 17‐ nor ‐cephalotane diterpenoids has been successfully established. Combining with bioinspired stereoselective dual hydrogenation, total synthesis (+)‐3‐deoxyfortalpinoid F, (+)‐harringtonolide, (−)‐fortalpinoids M/N/P, and analog (−)‐20‐deoxocephinoid P have achieved in 14–17 linear longest steps starting from commercially available materials.

Language: Английский

Unified Total Synthesis of Benzenoid and Troponoid Cephalotaxus Diterpenoids Enabled by Regiocontrolled Phenol-to-Tropone Ring Expansion DOI Creative Commons
Xu-cheng Gan,

Zi-An Zhang,

Xiaoyu Shi

et al.

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

3

Cephalotane diterpenoids: structural diversity, biological activity, biosynthetic proposal, and chemical synthesis DOI
Jin‐Xin Zhao,

Zhan‐Peng Ge,

Jian‐Min Yue

et al.

Natural Product Reports, Journal Year: 2024, Volume and Issue: 41(7), P. 1152 - 1179

Published: Jan. 1, 2024

Covering: up to the end of 2023Cephalotane diterpenoids are a unique class natural products exclusive genus Cephalotaxus, featuring rigid 7,6,5,6-fused tetracyclic architecture. The study cephalotanes dates back 1970s, when harringtonolide (1), Cephalotaxus troponoid with peculiar norditerpenoid carbon skeleton, was first discovered. In recent years, prototype C20 proposed as cephalotane were disclosed, which triggered intense studies on this diterpenoid family. To date, cumulative total 105 great structural diversity and biological importance have been isolated. addition, significant advances made in field synthesis biosynthesis years. This review provides complete overview chemical structures, bioactivities, biosynthetic aspects, completed all isolated diterpenoids, will help guide future research compounds.

Language: Английский

Citations

17

Divergent Synthesis of 17‐nor‐Cephalotane Diterpenoids through Developed Ynol‐diene Cyclization DOI
Zezhong Sun,

Xin Shu,

Fuli Ma

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: unknown

Published: Aug. 23, 2024

On the basis of a novel ynol-diene cyclization developed as rapid access to tropone unit, first divergent strategy 17-nor-cephalotane diterpenoids has been successfully established. Combining with bioinspired stereoselective dual hydrogenation, total synthesis (+)-3-deoxyfortalpinoid F, (+)-harringtonolide, (-)-fortalpinoids M/N/P, and analog (-)-20-deoxocephinoid P have achieved in 14-17 linear longest steps starting from commercially available materials.

Language: Английский

Citations

6

Salvicsite A-C: Three Seco-Norabietane Diterpenoids Including an Unusual Tetracyclic Skeleton from Salvia castanea Diels f. tomentosa Stib DOI

Lian-Yu Tang,

Liu-Nian-Qiu Wang,

M. Alemla Ao

et al.

The Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: 90(4), P. 1697 - 1705

Published: Jan. 21, 2025

Three seco-norabietane diterpenoids, salvicsites A-C (1-3), along with two known compounds, were isolated from the roots and rhizomes of Salvia castanea Diels f. tomentosa Stib. Salvicsite A (1) represents an unprecedented structural combination, featuring eight-membered α-methyl-α,β-unsaturated lactone ring a five-membered α,β-unsaturated ring, based on 6/6/5/8 system. Their structures elucidated through comprehensive spectroscopic analyses, X-ray crystallography, quantum chemical calculations. Putative biosynthetic pathways 1-3 proposed, compound 5 being plausible biogenetic precursor. The AChE inhibition assay demonstrated that salvicsite exhibited notable inhibitory effect against AChE, IC50 value 9.56 ± 1.05 μM. Enzymatic kinetic studies indicated acted as mixed-type inhibitor, its binding mode was explored molecular docking. results cytotoxic activity only activity.

Language: Английский

Citations

0

Diterpenes: Nature’s Hidden Gems of Immunomodulation DOI Open Access
Jonas S. Almeida, André Correa de Oliveira, Carlos Eduardo de Castro Alves

et al.

International Journal of Molecular Sciences, Journal Year: 2025, Volume and Issue: 26(5), P. 2250 - 2250

Published: March 3, 2025

Natural products, especially specific metabolites found in many medicinal plants, exhibit extensive therapeutic potential due to their diverse biological characteristics. Among these compounds, diterpenes stand out for active principles described phytochemical studies. Diterpenes immunomodulatory effects by influencing the production of cytokines and other signaling molecules involved immune response. These actions contribute achieving a more balanced profile. The ability selectively harmoniously modulate response positions compounds derived from natural products is promising research field development therapies. Due broad activities diterpenes, use molecular docking emerges as relevant tool quantitative screening large number substances. This review comprehensively examines pharmacological modulating system. It highlights existing experimental evidence supporting efficacy safety treatment dysfunctions. Ultimately, this aims new strategies field.

Language: Английский

Citations

0

Research on the Biomimetic Construction of Propeller-Shaped Dual Lactone Ring System in Cephalotanin B DOI
Zezhong Sun, Shuang Jin, Yunxia Wang

et al.

Chinese Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: 45(3), P. 996 - 996

Published: Jan. 1, 2025

Language: Английский

Citations

0

Visible-light-mediated site-selective C(sp2)–H alkylation of tropones facilitates semi-synthesis of cephafortunoids A and B DOI Creative Commons
Q. Zeng, Cheng‐Yu Zheng,

Zhan‐Peng Ge

et al.

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

Asymmetric total synthesis of benzenoid cephalotane-type diterpenoids through a cascade C(sp2) & C(sp3)–H activation DOI Creative Commons
Xiangxin Li, Zhiying Lu,

Shaocong Liu

et al.

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

Research Progress of Natural Active Substances with Immunosuppressive Activity DOI Creative Commons
Fei Shao, Qiying Shen, Zhengfei Yang

et al.

Molecules, Journal Year: 2024, Volume and Issue: 29(10), P. 2359 - 2359

Published: May 16, 2024

The increasing prevalence of autoimmune diseases globally has prompted extensive research and the development immunosuppressants. Currently, immunosuppressive drugs such as cyclosporine, rapamycin, tacrolimus have been utilized in clinical practice. However, long-term use these may lead to a series adverse effects. Therefore, there is an urgent need explore novel drug candidates for treating diseases. This review aims find potential candidate molecules natural compounds derived from plants, animals, fungi over past decade. These include terpenoids, alkaloids, phenolic compounds, flavonoids, others. Among them, 49, 151, 173, 200, 204, 247 excellent activity; their IC50 were less than 1 μM. A total 109 good activity, with ranging 10 active high medicinal potential. names, sources, structures, structure-activity relationship summarized analyzed.

Language: Английский

Citations

0

Unified chemical synthesis of cephalotaxus diterpenoids: A biosynthetic reversed strategy DOI

Yangyang Cheng,

Zhihua Ma, Hui Shao

et al.

Tetrahedron, Journal Year: 2024, Volume and Issue: 162, P. 134114 - 134114

Published: June 20, 2024

Language: Английский

Citations

0