Photochemical C–H Borylation in Organic Synthesis DOI Creative Commons
Supriya Rej, Stephanie G. E. Amos, Arjan W. Kleij

et al.

ACS Catalysis, Journal Year: 2025, Volume and Issue: 15(3), P. 1753 - 1770

Published: Jan. 16, 2025

Although C–H bond functionalization has been extensively studied since its discovery in 1955, the borylation of organic compounds by activating bonds only became popular valuable Hartwig 1995 who considered a wider application these transformations synthetic chemistry. For borylation, catalytic activation this generally low-reactivity can be performed many ways. Among approaches reported are use and stoichiometric reagents, thermal activation, photochemical suitable substrates. Iridium-, ruthenium-, rhodium-based protocols using have played crucial role toward establishment area. Photochemical though, scarcely explored despite fact that it represents comparably environmentally benign protocol light as renewable energy source. In literature survey, we highlight recent developments from initial inception up to latest advancements.

Language: Английский

Transition-Metal-Based Nanozymes: Synthesis, Mechanisms of Therapeutic Action, and Applications in Cancer Treatment DOI
Qinrui Fu,

Chuang Wei,

Mengzhen Wang

et al.

ACS Nano, Journal Year: 2024, Volume and Issue: 18(19), P. 12049 - 12095

Published: May 2, 2024

Cancer, as one of the leading causes death worldwide, drives advancement cutting-edge technologies for cancer treatment. Transition-metal-based nanozymes emerge promising therapeutic nanodrugs that provide a reference therapy. In this review, we present recent breakthrough First, comprehensively outline preparation strategies involved in creating transition-metal-based nanozymes, including hydrothermal method, solvothermal chemical reduction biomimetic mineralization and sol–gel method. Subsequently, elucidate catalytic mechanisms (catalase (CAT)-like activities), peroxidase (POD)-like oxidase (OXD)-like activities) superoxide dismutase (SOD)-like along with their activity regulation such morphology control, size manipulation, modulation, composition adjustment surface modification under environmental stimulation. Furthermore, elaborate on diverse applications anticancer therapies encompassing radiotherapy (RT), chemodynamic therapy (CDT), photodynamic (PDT), photothermal (PTT), sonodynamic (SDT), immunotherapy, synergistic Finally, challenges faced by are discussed alongside future research directions. The purpose review is to offer scientific guidance will enhance clinical based transition metals.

Language: Английский

Citations

53

Electronic Structure Design of Transition Metal-Based Catalysts for Electrochemical Carbon Dioxide Reduction DOI Creative Commons
Liang Guo, Jingwen Zhou, Fu Liu

et al.

ACS Nano, Journal Year: 2024, Volume and Issue: 18(14), P. 9823 - 9851

Published: March 28, 2024

With the increasingly serious greenhouse effect, electrochemical carbon dioxide reduction reaction (CO2RR) has garnered widespread attention as it is capable of leveraging renewable energy to convert CO2 into value-added chemicals and fuels. However, performance CO2RR can hardly meet expectations because diverse intermediates complicated processes, necessitating exploitation highly efficient catalysts. In recent years, with advanced characterization technologies theoretical simulations, exploration catalytic mechanisms gradually deepened electronic structure catalysts their interactions intermediates, which serve a bridge facilitate deeper comprehension structure-performance relationships. Transition metal-based (TMCs), extensively applied in CO2RR, demonstrate substantial potential for further modulation, given abundance d electrons. Herein, we discuss representative feasible strategies modulate catalysts, including doping, vacancy, alloying, heterostructure, strain, phase engineering. These approaches profoundly alter inherent properties TMCs interaction thereby greatly affecting rate pathway CO2RR. It believed that rational design modulation fundamentally provide viable directions development toward conversion many other small molecules.

Language: Английский

Citations

34

Research on transition metals for the multicomponent synthesis of benzo-fused γ-lactams DOI Creative Commons
Fadhil Faez Sead, Vicky Jain,

Suhas Ballal

et al.

RSC Advances, Journal Year: 2025, Volume and Issue: 15(4), P. 2334 - 2346

Published: Jan. 1, 2025

Benzo-fused γ-lactams are fundamental in medicinal chemistry, acting as essential elements for various therapeutic agents due to their structural adaptability and capability enhance biological activity.

Language: Английский

Citations

6

Stereoselective formation of boron-stereogenic organoboron derivatives DOI Creative Commons

Amel Abdou-Mohamed,

Clara Aupic,

Corentin Fournet

et al.

Chemical Society Reviews, Journal Year: 2023, Volume and Issue: 52(13), P. 4381 - 4391

Published: Jan. 1, 2023

Four-coordinate organoboron derivatives present interesting chemical, physical, biological, electronical, and optical properties. Given the increasing demand for synthesis of smart functional materials based on chiral compounds, exploration stereoselective boron-stereogenic organo-derivatives is highly desirable. However, construction compounds stereogenic at boron has been far less studied than other elements main group due to configurational stability concerns. Nowadays, these species are no longer elusive configurationally stable have highlighted. The idea show potential building four-coordinate centre encourage future endeavors developments in field.

Language: Английский

Citations

24

Radical hydroboration for the synthesis of organoboron compounds DOI
Yee Lin Phang, Ji‐Kang Jin, Feng‐Lian Zhang

et al.

Chemical Communications, Journal Year: 2024, Volume and Issue: 60(32), P. 4275 - 4289

Published: Jan. 1, 2024

This review describes the recent research on radical hydroboration, which covers different boron sources including N-heterocyclic carbene borane, bis(pinacolato)diboron and pinacolborane, as well strategies in boryl generation.

Language: Английский

Citations

12

Diversified Synthesis of Chiral Fluorinated Cyclobutane Derivatives Enabled by Regio‐ and Enantioselective Hydroboration DOI

Fushan Yuan,

Xingyu Qi,

Yuanyue Zhao

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(23)

Published: April 2, 2024

The diversified synthesis of chiral fluorinated cyclobutane derivatives has remained a difficult task in synthetic chemistry. Herein, we present an approach for asymmetric hydroboration and formal hydrodefluorination gem-difluorinated cyclobutenes through rhodium catalysis, providing α-boryl cyclobutanes monofluorinated with excellent regio- enantioselectivity, respectively. key to the success two transformations relies on efficient, mild highly selective rhodium-catalyzed HBPin (pinacolborane), which subsequent addition base, catalytic amount palladium some cases, results formation products four-membered ring retained. obtained are versatile building blocks that provide platform enantioenriched great diversity.

Language: Английский

Citations

11

Triethoxysilane-Catalyzed Single and Sequential Regioselective Hydroboration of Terminal Alkynes: Sustainable Access to E-Alkenylboronate and Alkyl Gem-Diboronate Esters by Non-Covalent Interactions DOI

Harleen Kaur,

Himani Ahuja,

Rebeca Arévalo

et al.

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 976 - 981

Published: Jan. 1, 2025

Triethoxysilane was found to be an efficient catalyst for the synthesis of E-alkenyl- and alkyl-di-boronate esters by single sequential hydroboration terminal alkynes, respectively, with pinacolborane. Mechanistic studies support that formation diboronate proceeds a double pathway steric electronic profile at Si being key enabling second step. Weak non-covalent interactions involving C≡C or C═C bonds in alkynes alkenylboronate have been identified as responsible substrate activation toward addition HBPin.

Language: Английский

Citations

1

Mechanochemical Synthesis of α‐halo Alkylboronic Esters DOI Creative Commons

Yunyi Zhao,

Zekun Yang, Xin Wang

et al.

Advanced Science, Journal Year: 2024, Volume and Issue: 11(33)

Published: July 3, 2024

α-halo alkylboronic esters, acting as ambiphilic synthons, play a pivotal role versatile intermediates in fields like pharmaceutical science and organic chemistry. The sequential transformation of carbon-boron carbon-halogen bonds into broad range carbon-X allows for programmable bond formation, facilitating the incorporation multiple substituents at single position streamlining synthesis complex molecules. Nevertheless, synthetic potential these compounds is constrained by limited reaction patterns. Additionally, conventional methods often necessitate use bulk toxic solvents, exhibit sensitivity to air/moisture, rely on expensive metal catalysts, involve extended times. In this report, ball milling technique introduced that overcomes limitations, enabling external catalyst-free multicomponent coupling aryl diazonium salts, alkenes, simple halides. This approach offers general straightforward method obtaining diverse array thereby paving way extensive utilization synthons fine chemicals.

Language: Английский

Citations

6

Interweaving catalysis and cancer using Ru- and Os-arene complexes to alter cellular redox state: A structure-activity relationship (SAR) review DOI
Srividya Swaminathan,

Rajasekharan Jayakumari Deepak,

Ramasamy Karvembu

et al.

Coordination Chemistry Reviews, Journal Year: 2023, Volume and Issue: 491, P. 215230 - 215230

Published: June 2, 2023

Language: Английский

Citations

16

Iron-Catalyzed Selective Hydroboration of CO2 by Cooperative B–H Bond Activation DOI

Hongjie Gao,

Jiong Jia,

Chen‐Ho Tung

et al.

Organometallics, Journal Year: 2023, Volume and Issue: 42(10), P. 944 - 951

Published: May 9, 2023

We report a novel iron(II) complex supported by an anionic phosphanyl-iminopyridinate ligand, Cp*Fe(Cy2PN═C5H4N) (1), which shows remarkable catalytic activity in the selective hydroboration of CO2 with HBpin, producing boryl formate turnover frequency (TOF) ∼1176 h–1 at room temperature. This catalysis involves cooperative metal–ligand reactivity for H–B bond activation, affording key Fe(II)–H intermediate, Cp*FeH(Cy2PN(Bpin)C5H4N) (2), that binds Bpin moiety non-coordinated amino site. The very fast and formoxy production can be conveniently coupled to N-formylation amines, delivers variety formamides. In addition, reduction CH3OBpin stage was also achieved 1 HBpin under N2.

Language: Английский

Citations

13