Recent Progresses in Two‐Dimensional Carbon‐Metal Composites for Catalysis Applications DOI
Yongjie Zhang, Kah Meng Yam, Hao Wang

et al.

Wiley Interdisciplinary Reviews Computational Molecular Science, Journal Year: 2025, Volume and Issue: 15(2)

Published: March 1, 2025

ABSTRACT Catalysis stands as a cornerstone for the global economy and human society, with metals metal oxides assuming significant roles in catalytic research. The emergence of two‐dimensional (2D) carbon materials, such graphene (GR), graphyne (GY), graphdiyne (GDY), boasting unique structural tunable electronic properties, opens up new avenues exploration heterogeneous catalysts. In this review, we initially analyze limitations inherent metal‐ oxide‐based Subsequently, present an overview latest advancements catalysts pertaining to 2D carbon‐metal composites. We categorize these composites into two groups: support‐induced disordered lattices metal‐carbon crystals. realm predominantly encompasses GR‐, GY‐, GDY‐supported single‐atom (SACs), dual‐atom (DACs), single‐cluster (SCCs). Meanwhile, domain crystals primarily includes organic frameworks (MOFs), transition carbides (MXenes), graphite (g‐MCs). This review encapsulates comprehensive understanding structure, stability, application all from theoretical standpoint, placing particular emphasis on coordination structure –performance relationship. To conclude, brief summary outlook are provided, offering insights future study

Language: Английский

Asymmetric Synthesis of Trisubstituted Vicinal Diols through Copper(I)‐Catalyzed Diastereoselective and Enantioselective Allylation of Ketones with Siloxypropadienes DOI
Nan Jiang,

Pei‐Zhi Liu,

Zhi‐Zhou Pan

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(21)

Published: Feb. 27, 2024

Chiral trisubstituted vicinal diols are a type of important organic compounds, serving as both common structure units in bioactive natural products and chiral auxiliaries asymmetric synthesis. Herein, by using siloxypropadienes the precursors allyl copper(I) species, copper(I)-catalyzed diastereoselective enantioselective reductive allylation ketones was achieved, providing syn-diols anti-diols good to excellent enantioselectivity. DFT calculations show that cis-γ-siloxy-allyl copper species generated favorably with either 1-TBSO-propadiene or 1-TIPSO-propadiene. Moreover, steric difference TBS group TIPS distinguishes face selectivity acetophenone, leading syn-selectivity for anti-selectivity Easy transformations were performed, demonstrating synthetic utility present method. one diol prepared above used suitable organocatalyst catalytic self-coupling aldimines situ B

Language: Английский

Citations

8
A Cytochrome P450 Enzyme Catalyses Oxetane Ring Formation in Paclitaxel Biosynthesis DOI

Changkang Li,

Xinxin Yin,

Shuai Wang

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(31)

Published: May 7, 2024

Oxetane synthase (TmCYP1), a novel cytochrome P450 enzyme from Taxus×media cell cultures, has been functionally characterized to efficiently catalyse the formation of oxetane ring in tetracyclic taxoids. Transient expression TmCYP1 Nicotiana benthamiana using 2α,5α,7β,9α,10β,13α-hexaacetoxytaxa-4(20),11(12)-diene (1) as substrate led production major derivative, 1β-dehydroxybaccatin IV (1 a), and minor 4β,20-epoxide baccatin I b). However, feeding decinnamoyltaxinine J (2), 5-deacetylated derivative 1, yielded only 5α-deacetylbaccatin (2 b), 4β,20-epoxide. A possible reaction mechanism was proposed on basis substrate-feeding,

Language: Английский

Citations

8
Divergent Synthesis of Scabrolide A and Havellockate via an exo-exo-endo Radical Cascade DOI
Peng Chen, Quanping Guo,

Guo-Xiong Xu

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(21), P. 14422 - 14426

Published: May 6, 2024

Here we report a concise and divergent synthesis of scabrolide A havellockate, representative members polycyclic marine natural product furano(nor)cembranoids. The features highly efficient exo-exo-endo radical cascade. Through the generation two rings, three C–C bonds, contiguous stereocenters in one step, this remarkable transformation not only assembles bowl-shaped, common 6–5–5 fused ring system from simple building blocks but also precisely installs functionalities at desired positions sets stage for further preparation both target molecules. Further studies reveal that robust unusual 6-endo addition cascade is likely facilitated by rigidity substrate.

Language: Английский

Citations

6
Total Synthesis of Taxol Enabled by Intermolecular Radical Coupling and Pd-Catalyzed Cyclization DOI
Takahiro Watanabe,

Kyohei Oga,

Hiroaki Matoba

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(47), P. 25894 - 25902

Published: Nov. 16, 2023

Taxol (1) is a clinically used antineoplastic diterpenoid. The tetracyclic ring system comprises 6/8/6-membered carbocycle (ABC-ring) and fused oxetane (D-ring) embedded with bridgehead double bond decorated multiple oxygen functionalities. Here, we report convergent total synthesis of this exceedingly complex natural product. C-ring fragment was designed to possess bromocyclohexenone an extra tetrahydrofuran control the reactivity selectivity, as well minimize functional group manipulations en route 1. α-alkoxyacyl telluride A-ring served radical precursor, intermolecular coupling realized installation C2- C3-stereocenters reductive removal bromide. After C8-quaternary stereocenter constructed by exploiting three-dimensional shape intermediate, C11-vinyl triflate C8-methyl ketone were utilized for Pd(0)-catalyzed cyclization central eight-membered B-ring olefin. Adjustment oxidation level attachment D-ring completed 1 (28 steps, longest linear sequence). design principle implementation powerful reaction described in present provide valuable information planning executing syntheses diverse densely oxygenated terpenoids.

Language: Английский

Citations

14
Regioselective synthesis of N-containing polycyclic compounds via radical annulation cyclization of 1,7-dienes with aldehydes DOI

Jia-Li Sui,

Long‐Jin Zhong, Biquan Xiong

et al.

Chemical Communications, Journal Year: 2024, Volume and Issue: 60(36), P. 4834 - 4837

Published: Jan. 1, 2024

A convenient method for oxidant-promoted radical cascade acylation or decarbonylative alkylation of 1,7-dienes with aldehydes the construction tetracyclic N-containing skeletons has been established.

Language: Английский

Citations

5
Historical Perspective and Current Trends in Anticancer Drug Development DOI Open Access
Katarzyna Gach, Joanna Drogosz-Stachowicz, Anna Janecka

et al.

Cancers, Journal Year: 2024, Volume and Issue: 16(10), P. 1878 - 1878

Published: May 15, 2024

Cancer is considered one of the leading causes death in 21st century. The intensive search for new anticancer drugs has been actively pursued by chemists and pharmacologists decades, focusing either on isolation compounds with cytotoxic properties from plants or screening thousands synthetic molecules. Compounds that could potentially become candidates must have ability to inhibit proliferation and/or induce apoptosis cancer cells without causing too much damage normal cells. Some were discovered accident, others as a result long-term research. In this review, we presented brief history development most important groups drugs, pointing fact they all many side effects.

Language: Английский

Citations

5
Type I [4σ+4π] versus [4σ+4π−1] Cycloaddition To Access Medium‐Sized Carbocycles and Discovery of a Liver X Receptor β‐Selective Ligand DOI
Cheng Jiang,

Lingfei Hu,

Shuna Shen

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(28)

Published: April 22, 2024

Transition-metal-catalyzed [4+4] cycloaddition leading to cyclooctanoids has centered on dimerization between 1,3-diene-type substrates. Herein, we describe a [4σ+4π-1] and [4σ+4π] strategy access 7/8-membered fused carbocycles through rhodium-catalyzed coupling the 4σ-donor (benzocyclobutenones) pendant diene (4π) motifs. The two pathways can be controlled by adjusting solvated CO concentration. A broad range (>40 examples) of 5-6-7 5-6-8 polyfused was obtained in good yields (up 90 %). DFT calculations, kinetic monitoring

Language: Английский

Citations

4
Post-genomic illumination of paclitaxel biosynthesis DOI
Alisdair R. Fernie, Fang Liu, Youjun Zhang

et al.

Nature Plants, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 27, 2024

Language: Английский

Citations

4
Total Syntheses of Highly Oxidized Natural Products† DOI Open Access
Yan Wang, Xiangbing Qi

Chinese Journal of Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 3, 2025

Comprehensive Summary Natural products with high oxidation states and complex chemical skeletons exhibit diverse bioactivities due to their unique interactions biological targets. The state is characterized by the presence of multiple oxygen‐containing functional groups such as hydroxyl groups, carbonyl epoxides that are usually tough construct selectively. In recent years, thanks development efficient strategies sophisticated methodologies, significant advancements have been made in total syntheses highly oxidized natural (HONPs). this review, we highlight examples HONPs focusing on tetrodotoxin (TTX) its derivatives, steroidal alkaloids, sesquiterpenes, diterpenoids since 2019. Key Scientists 2005, Yang group applied thioureas ligands Pauson−Khand reaction for synthesis triterpene products. methodological advances achieved a series topologically structural features following years. 2009, Baran established pioneering “two‐phase” approach terpenes, an innovative strategy has inspired numerous field. 2011, Xu Theodorakis (−)‐jiadifenolide, sesquiterpene from Illicium . 2012, Li 6π electrocyclization containing aromatic rings. 2014, Inoue introduced α‐alkoxy bridgehead radical, facilitating unified ryanodane diterpenoids. subsequent radical‐based convergent were employed assembling HONPs. developed type ΙΙ [5+2] reaction, which can be efficiently featuring bridged ring systems. Reisman presented pattern analysis guided synthetic designs complex, isoryanodane diterpenes. 2017, Gao reported photoenolization/Diels‐Alder (PEDA) constructing related polycyclic rings elevated states. 2018, Ding unprecedented oxidative dearomatization‐induced (ODI) cycloaddition/pinacol‐ 1,2‐acyl migration cascade assemble oxygenated bicyclo[3.2.1]octane system, was subsequently grayanane same year, Gui explored “bioinspired” strategic transformations enabled rapid construction core framework steroid terpenoid 2020, Luo successfully synthesized several HONPs, including (−)‐batrachotoxinin, (−)‐zygadenine, diterpenoids, employing elegant strategies. 2021, Zhang site‐specific photochemical desaturation late‐stage skeletal reorganization strategies, enabling divergent sesquiterpenes. 2022, Jia first (−)‐principinol C, accomplished six More recently, Trauner concise tetrodotoxin, particularly strategy.

Language: Английский

Citations

0
A Tricyclo[4.3.1]decane Diterpenoid Skeleton from Croton laui: Isolation and 1H NMR-Based Metabolomic Profiling DOI
Qing Li,

Chen-Sen Xu,

Hao-Lin Yu

et al.

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: April 10, 2025

Lauicyclone A (1), a new skeletal diterpenoid characterized by an unprecedented carbon skeleton, represents the first reported natural product featuring complex tricyclo[4.3.1]decane framework. Along with Lauicyclones B-E (2-5), all five compounds were isolated from Croton laui. Comprehensive spectroscopic analyses, quantum-chemical calculations, and X-ray diffractions used to identify their structures. The antitumor mechanism of compound 1 was investigated using 1H NMR-based metabolomics.

Language: Английский

Citations

0