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

Late-stage benzenoid-to-troponoid skeletal modification of the cephalotanes exemplified by the total synthesis of harringtonolide DOI Creative Commons
Stefan Wiesler, Goh Sennari, Mihai V. Popescu

et al.

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: May 15, 2024

Abstract Skeletal modifications enable elegant and rapid access to various derivatives of a compound that would otherwise be difficult prepare. They are therefore powerful tool, especially in the synthesis natural products or drug discovery, explore different improve properties candidate starting from common intermediate. Inspired by biosynthesis cephalotane products, we report here single-atom insertion into framework benzenoid subfamily, providing troponoid congeners — representing reverse proposed (i.e., contra-biosynthesis approach). Computational evaluation our designed transformation prompted us investigate Büchner–Curtius–Schlotterbeck reaction p -quinol methylether, which ultimately results harringtonolide two steps cephanolide A, had previously prepared. Additional computational studies reveal unconventional selectivity outcomes driven choice Lewis acid nucleophile, should inform further developments these types reactions.

Language: Английский

Citations

9
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

1
Total Synthesis of Cephanolide A and Harringtonolide: A Unified Strategy Connecting Benzenoid and Troponoid Cephalotaxus Diterpenoids DOI Creative Commons

Zi-An Zhang,

Xu-cheng Gan,

Guang Tian

et al.

Published: Feb. 14, 2024

The fascinating benzenoid and troponoid Cephalotaxus diterpenoids are highly related biosynthetically, both of which popular targets for total synthesis. Herein, we describe a unified strategy the concise synthesis cephanolide A harringtonolide in 14 16 steps respectively. Palladium catalyzed Csp2-Csp3 cross-coupling followed by doubly electron-deficient intramolecular Diels-Alder reaction secure rapid construction carbon framework. Late-stage benzenoid-to-troponoid ring expansion was accomplished employing Büchner-Curtius-Schlotterbeck (BCS) reaction, furnishing two from A. This work shed light on chemical synthetic connection between diterpenoids.

Language: Английский

Citations

7
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
Divergent Synthesis of 17-nor-Cephalotane Diterpenoids through Developed Ynol-diene Cyclization DOI Creative Commons
Zezhong Sun,

Xin Shu,

Fuli Ma

et al.

Published: April 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.

Language: Английский

Citations

1
Divergent Synthesis of 17-nor-Cephalotane Diterpenoids through Developed Ynol-diene Cyclization DOI Creative Commons
Zezhong Sun,

Xin Shu,

Fuli Ma

et al.

Published: April 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.

Language: Английский

Citations

1
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