Photocatalytic [3+2] Cycloaddition of Alkyl/aryl Iodides and Internal Alkynes by Merging Halogen and Hydrogen Atom Transfer DOI Creative Commons
Zhenyu Gu,

Rong Jia,

Tianqing Zeng

et al.

Chinese Journal of Chemistry, Journal Year: 2024, Volume and Issue: 42(19), P. 2329 - 2334

Published: May 22, 2024

Comprehensive Summary A visible light photocatalytic [3+2] cycloaddition of alkynes with readily accessible organic iodides as the C3 synthon is developed herein. By merging halogen atom transfer (XAT) and hydrogen (HAT), alkyl/aryl serve a formal diradical precursor add across C‐C triple bonds to deliver number functionalized cyclopentanes in moderate high yields exceptional regio‐ diastereoselectivity. reductive radical‐polar crossover mechanism, involving cascade XAT, radical addition, 1,5‐HAT, polar effect‐promoted 5‐endo annulation, single electron (SET) reduction, protonation, may account for this unprecedented dehalogenative cycloaddition. This work not only expands repertoire traditional RATC methodology, but also provides robust platform expedient assembly cyclopentanes, valuable structural motif realms medicinal chemistry material sciences.

Language: Английский

Contact-electro-catalysis (CEC) DOI
Ziming Wang, Xuanli Dong, Wei Tang

et al.

Chemical Society Reviews, Journal Year: 2024, Volume and Issue: 53(9), P. 4349 - 4373

Published: Jan. 1, 2024

Contact-electro-catalysis (CEC) is an emerging field that utilizes electron transfer occurring at the liquid–solid and even liquid–liquid interfaces because of contact-electrification effect to stimulate redox reactions.

Language: Английский

Citations

49

Photoinduced Selective B–H Activation of nido-Carboranes DOI

Sheng‐Wen Xu,

Hongjian Zhang, Jingkai Xu

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(11), P. 7791 - 7802

Published: March 10, 2024

The development of new synthetic methods for B–H bond activation has been an important research area in boron cluster chemistry, which may provide opportunities to broaden the application scope clusters. Herein, we present a reaction strategy direct site-selective functionalization nido-carboranes initiated by photoinduced cage via noncovalent cage···π interaction. As result, nido-carborane radical is generated through single electron transfer from 3D 2D photocatalyst upon irradiation with green light. resulting transient could be directly probed advanced time-resolved EPR technique. In air, subsequent transformations active have led efficient and selective B–N, B–S, B–Se couplings presence N-heterocycles, imines, thioethers, thioamides, selenium ethers. This protocol also facilitates both late-stage modification drugs synthesis nido-carborane-based drug candidates neutron capture therapy (BNCT).

Language: Английский

Citations

15

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

Boryls, their compounds and reactivity: a structure and bonding perspective DOI Creative Commons
Xueying Guo, Zhenyang Lin

Chemical Science, Journal Year: 2024, Volume and Issue: 15(9), P. 3060 - 3070

Published: Jan. 1, 2024

Boryls and their compounds are important due to diverse range of applications in the fields materials science catalysis. They an integral part boron chemistry, which has attracted tremendous research interest over past few decades. In this perspective, we provide in-depth analysis reaction chemistry boryl from a structure bonding perspective. We discuss reactivity boryls various transition metal complexes diborane(4) towards different substrate molecules, with focus on nucleophilic electrophilic properties processes. Additionally, briefly radicals. Our sheds new light unique potential for catalytic applications.

Language: Английский

Citations

10

Photoinduced Electron Donor Acceptor Complex‐Enabled α‐C(sp3)−H Alkenylation of Amines DOI

Jianzhong Lu,

Kaiyao Yuan,

Jia-Lian Zheng

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(44)

Published: July 13, 2024

Allylic amines are prevalent and vital structural components present in many bioactive compounds natural products. Additionally, they serve as valuable intermediates building blocks, with wide-ranging applications organic synthesis. However, direct α-C(sp

Language: Английский

Citations

10

Photocatalytic Direct Borylation of Benzothiazole Heterocycles via a Triplet Activation Strategy DOI

Ze‐Le Chen,

Claire Empel, Yang Xie

et al.

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

Published: Jan. 11, 2025

Boron compounds are widely employed in organic chemistry, pharmaceuticals, and materials science. Among them, borylated heterocycles serve as versatile synthons for the construction of new C-C or C-heteroatom bonds via coupling radical processes. Such methods direct C-H borylation reactions high synthetic value to reduce number steps amount waste improve efficiency. Despite significant advances, remains an ongoing challenge with great potential applications chemical synthesis. Herein, we describe a photocatalytic reaction five-membered ring by employing stable N-heterocyclic carbene borane borylating reagent photoredox catalyst. Under green mild conditions, was achieved on series benzo-fused heterocyclic compounds. Further studies demonstrate utility this approach pharmaceutical agrochemical research.

Language: Английский

Citations

2

Dative Bonding Activation Enables Precise Functionalization of the Remote B–H Bond of nido-Carborane Clusters DOI
Hongyuan Ren, Ningning Zhou, Wenli Ma

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: unknown

Published: Sept. 13, 2024

The innovation of synthetic strategies for selective B-H functionalization is a pivotal objective in the realm boron cluster chemistry. However, precise, efficient, and rapid bond carboranes that distant from existing functional groups remains intractable owing to limited approaches site-selective control established methods. Herein, we report dative bonding activation strategy nonclassical remote site

Language: Английский

Citations

8

Dearomative 1,4-Difunctionalization of Non-Activated Arenes Enabled by Boryl Radical-Mediated Halogen-Atom Transfer DOI
Chengliang Deng, Hao Wu,

Sheng Li

et al.

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 1294 - 1304

Published: Jan. 7, 2025

Given the widespread presence of spirocyclic scaffolds in natural products and pharmacologically relevant synthetic compounds, development efficient methodologies for their construction holds great importance medicinal chemistry pharmaceutical research. In this study, a general photochemical dearomative spirocyclization nonactivated arenes has been established. The key to method lies ability amine-borane radicals activate aryl bromides iodides via halogen-atom transfer, thereby allowing conversion halides into corresponding subsequent chemodivergent transformations. remarkable compatibility versatility 1,4-difunctionalization is showed by rapid assembly structurally diverse 1,4-cyclohexadiene-based spirocycles incorporating oxindole, indoline, or dihydrobenzofuran subunits. Moreover, potential utility protocol exemplified formal total synthesis vasopressin V2 receptor antagonist Satavaptan.

Language: Английский

Citations

1

Recent advances in hydrogen atom transfer induced C(sp3)–H functionalizations initiated by radical addition to alkynes DOI
Yulu Zhou, Zhenyu Gu,

Yuwei Hong

et al.

Organic Chemistry Frontiers, Journal Year: 2023, Volume and Issue: 11(4), P. 1232 - 1250

Published: Dec. 28, 2023

Recent advances in HAT-induced C(sp 3 )–H functionalizations triggered by radical addition to alkynes, including 5- exo-trig , endo-trig 4- and 6- cyclization cascades, intermolecular functionalizations, are summarized.

Language: Английский

Citations

15

Rapid Prediction of Energy Level Alignment and Conductance of Single‐Molecule Junctions Through Intramolecular Dipole Moment DOI

Yirong Zhang,

Sha Yang, Yang Yang

et al.

Advanced Functional Materials, Journal Year: 2024, Volume and Issue: unknown

Published: April 4, 2024

Abstract How substituents affect the conductance of single‐molecule junctions has been a subject ongoing debate. Here, comparative study on transport properties across broader range experimentally proposed and representative π‐conjugated molecular systems, each characterized by prototypical backbone motifs with distinct terminal groups featuring is conducted. Employing non‐equilibrium Green's function method within density functional theory, this investigation reveals significant impact junction due to asymmetric characteristics arising from both electronic spatial effects induced di‐substituents phenanthrene analogs C═C or B─N motifs. Remarkably, linear correlation uncovered, either negative positive, between dipole moment molecules conductance, contingent upon whether governed highest occupied orbital (HOMO) lowest unoccupied (LUMO) states. Furthermore, validity descriptor substantiated various substituted series, including 2,7‐dipyridylfluorene, oligo(phenylene ethynylene), 1,4‐diaminobenzene. These findings underscore pivotal role individual moment, easily determinable, in offering precise predictive insight into intricate junctions.

Language: Английский

Citations

5