Organophotocatalyst Enabled Deoxycyclopropanation of Alcohols DOI Creative Commons
Yongsheng Zhang,

Jincheng Wang,

Xiaoyan He

et al.

Advanced Science, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 29, 2024

Abstract Cyclopropane fragments, which widely exist in marketed drugs and natural products, can confer special pharmacological properties to small‐molecule drugs. Therefore, developing methods construct cyclopropanes is of great significance. Nevertheless, the introduction cyclopropane primarily relies on already‐formed cyclopropyl groups, significantly restricts diversity skeletons. Late‐stage direct cyclopropanation still a challenging task. Herein, photo‐induced intermolecular deoxycyclopropanation reaction that employs alcohols as substrates, 1 mol.% 2,3,5,6‐tetrakis(carbazol‐9‐yl)‐1,4‐dicyanobenzene (4CzTPN) organophotocatalyst reported. This method proceeds with high transformation efficiency (up 98% yield) exhibits broad functional group tolerance, such primary, secondary, tertiary well various activated β‐halogenated alkenes. process mild, easy operate, has low equipment requirements. The power this technology demonstrated by late‐stage functionalization five products.

Language: Английский

Visible Light-Induced Reactions of Diazo Compounds and Their Precursors DOI
Ziyan Zhang, Vladimir Gevorgyan

Chemical Reviews, Journal Year: 2024, Volume and Issue: 124(11), P. 7214 - 7261

Published: May 16, 2024

In recent years, visible light-induced reactions of diazo compounds have attracted increasing attention in organic synthesis, leading to improvement existing reactions, as well the discovery unprecedented transformations. Thus, photochemical or photocatalytic generation both carbenes and radicals provide milder tools toward these key intermediates for many valuable However, vast majority transformations represent new reactivity modes compounds, which are achieved by decomposition photoredox catalysis. particular, use a redox-active photocatalysts opens avenue plethora radical reactions. The application methods led inaccessible classical associated with metal carbenes. most cases, act sources but can also serve acceptors. Importantly, described processes operate under mild, practical conditions. This Review describes this subfield compound chemistry, particularly focusing on advancements.

Language: Английский

Citations

60
The Carbene Chemistry of N-Sulfonyl Hydrazones: The Past, Present, and Future DOI
Xiaolong Zhang, Paramasivam Sivaguru,

Yongzhen Pan

et al.

Chemical Reviews, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 10, 2025

N-Sulfonyl hydrazones have been extensively used as operationally safe carbene precursors in modern organic synthesis due to their ready availability, facile functionalization, and environmental benignity. Over the past two decades, there has tremendous progress chemistry of N-sulfonyl presence transition metal catalysts, under metal-free conditions, or using photocatalysts photoirradiation conditions. Many transfer reactions are unique cannot be achieved by any alternative methods. The discovery novel development highly enantioselective new skeletal editing represent notable recent achievements hydrazones. This review describes overall made hydrazones, organized based on reaction types, spotlighting current state-of-the-art remaining challenges addressed future. Special emphasis is devoted identifying, describing, comparing scope limitations methodologies, key mechanistic scenarios, potential applications complex molecules.

Language: Английский

Citations

6
Visible-Light-Induced [4 + 3]-Annulation of Carbonyl Ylides with Alkenyl Pyrazolinone for Constructing [4.2.1]-Oxo-Bridged Oxocine Skeleton DOI

Dong-Sheng Ji,

Xin Zhang,

Peiqin Zhang

et al.

Organic Letters, Journal Year: 2025, Volume and Issue: 27(2), P. 709 - 714

Published: Jan. 7, 2025

Herein, we present a visible-light-induced protocol for the synthesis of highly functionalized oxo-bridged oxocine skeletons. This method generates carbenes via ortho-acyl diazo compounds, which are rapidly intercepted by oxygen atom an intermolecular acyl group to form cyclic 1,3-dipole. The in situ generated reactive 1,3-dipole undergoes facile formal [4 + 3] cycloaddition with alkenyl pyrazolinone, yielding [4.2.1]-oxo-bridged compounds.

Language: Английский

Citations

2
A visible-light-promoted metal-free approach for N–H insertions by using donor/donor diazo precursors DOI Creative Commons
Yu Zhang, Qiannan Li, Ping Wang

et al.

Green Chemistry, Journal Year: 2024, Volume and Issue: 26(8), P. 4600 - 4608

Published: Jan. 1, 2024

A metal-free and catalyst-free strategy is reported to achieve N–H insertions by coupling N -tosylhydrazones with diverse amines including aminopyridines, anilines, aliphatic amines, other nucleophiles such as imidazoles indoles.

Language: Английский

Citations

11
Photosensitized Reductive Elimination of Gold(III) to Enable Esterification of Aryl Iodides with Carboxylic Acids DOI Creative Commons
Jiawen Wu,

Wenqian Du,

Lizhu Zhang

et al.

JACS Au, Journal Year: 2024, Volume and Issue: 4(8), P. 3084 - 3093

Published: July 25, 2024

Compared to the well-established transition metal-catalyzed cross-coupling reactions, Au(I)/Au(III)-catalyzed reactions have lagged behind. Despite some advancements, achieving gold-catalyzed C-O coupling with carboxylic acids via an Au(III) carboxylate intermediate remains challenging due thermal unfavorability of critical reductive elimination step. Here, we present first photosensitized gold(III) enable esterification aryl iodides acids. In presence a (P, N)-gold(I) catalyst and photosensitizer benzophenone under blue LED irradiation, derivatives were obtained from both alkyl (1°, 2°, 3°) Mechanistic modeling studies support that energy transfer (EnT) produces excited-state complex couples This photoinduced energy-transfer strategy has been applied in several other gold catalysis indicating its potential for further applications.

Language: Английский

Citations

10
Visible-Light-Mediated Three-Component Strategy for the Synthesis of Isoxazolines and Isoxazoles DOI
Yanchuan Li, Yu Zhang, Jinxin Wang

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(15), P. 3130 - 3134

Published: April 8, 2024

Isoxazolines and isoxazoles commonly serve as core structures of many therapeutic agents natural products. However, the metal-free catalysis-free strategy for synthesis these privileged motifs at room temperature remains a challenging task. Herein, we report three-component to afford diverse isoxazolines via [3 + 2] cycloadditions in situ-formed nitronates olefins/alkynes under visible-light irradiation.

Language: Английский

Citations

9
Visible-light-induced [3+2] cycloadditions of donor/donor diazo intermediates with alkenes to achieve (spiro)-pyrazolines and pyrazoles DOI Creative Commons
Yu Zhang, Yanchuan Li, Shao‐Fei Ni

et al.

Chemical Science, Journal Year: 2023, Volume and Issue: 14(38), P. 10411 - 10419

Published: Jan. 1, 2023

To date, [3 + 2] cycloadditions of diazo esters with alkynes or alkenes have been a robust tool to generate pyrazoles and pyrazolines. However, methods capable generating donor/donor species from readily available N-tosylhydrazones furnish cycloadditions, remain elusive. Herein, we describe the first visible-light-induced precursors afford novel (spiro)pyrazolines bearing quaternary center. This protocol shows tolerable substrate scope covering versatile carbonyl compounds alkenes. Late-stage functionalization bioactive molecules, one-pot approach, gram-scale synthesis also introduced successfully prove practicability. At last, mechanistic experiments DFT studies suggested formation non-covalent interactions enabling activation intermediates.

Language: Английский

Citations

19
Light-induced arylation (alkylation) of N-sulfonylhydrazones with boronic acids DOI

Mohammad Junaid,

Sharma Happy,

Dongari Yadagiri

et al.

Chemical Communications, Journal Year: 2024, Volume and Issue: 60(20), P. 2796 - 2799

Published: Jan. 1, 2024

We report light-induced arylation (alkylation) for the synthesis of diarylmethanes, bis(diarylmethyl)benzenes, arylalkylmethanes, and triarylmethanes from readily accessible N -sulfonylhydrazones aryl/alkylboronic acids with aid Cs 2 CO 3 .

Language: Английский

Citations

6
Silver‐Catalyzed Dearomative Skeletal Editing of Indazoles by Donor Carbene Insertion DOI
Linxuan Li, Hongzhu Chen, Menglin Liu

et al.

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: 30(16)

Published: Jan. 11, 2024

Abstract Given the prevalence of heterocyclic scaffolds in drug‐related molecules, converting these highly modular into structural diversified and dearomatized analogs is an ideal strategy for improving their physicochemical pharmacokinetic properties. Here, we described efficient method silver carbene‐mediated dearomative N−N bond cleavage leading to skeletal hopping between indazole 1,2‐dihydroquinazoline via a selective single‐carbon insertion procedure. Using this methodology, series dihydroquinazoline analogues with diarylmethylene‐substituted quaternary carbon centers were constructed excellent yields good functional group compatibility, which was further illustrated by late‐stage diversification important pharmaceutically active ingredients. DFT calculations indicated that catalyst not only induces formation carbene, but also activates diazahexatriene intermediate, plays crucial role C−N bond.

Language: Английский

Citations

5
Synthesis of Difluorocyclopropanes via Visible‐Light‐Mediated [1+2] Cycloaddition of Diazo Esters with gem‐Difluoroalkenes and Evaluation of their Antifungal Activity DOI
Donghua Du, Chang Ji,

Shaoying Zheng

et al.

Advanced Synthesis & Catalysis, Journal Year: 2024, Volume and Issue: 366(8), P. 1738 - 1743

Published: Feb. 17, 2024

Abstract In this work, we reported a method for construction of difluorocyclopropanes through visible light‐promoted [1+2] cycloaddition reaction aryl diazo esters with gem ‐difluoroalkenes. The proceeds under mild conditions, encompasses wide range substrates (36 examples), exhibits good tolerance to various substituents, and demonstrates diastereoselectivity >20:1. Additionally, antifungal activity evaluation revealed that these derivatives exhibited certain activity, the EC 50 values products towards Botrytis cinerea Rhizoctonia solani were measured be 1.51 1.36 μM, respectively, which are significantly lower than those commercial fungicides Hymexazol Azoxystrobin. This work not only provides an efficient synthesis difluorocyclopropanyl derivatives, but reveals their potential applications in fungicide creation.

Language: Английский

Citations

5