Visible‐Light‐Mediated Activation of Remote C(sp3)‐H Bonds by Carbon‐Centered Biradical via Intramolecular 1,5‐ or 1,6‐Hydrogen Atom Transfer DOI

Xin-Tao Gu,

Jiahao Shen,

Ziyu Xu

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(38)

Published: June 21, 2024

In this study, we introduce a novel intramolecular hydrogen atom transfer (HAT) reaction that efficiently yields azetidine, oxetane, and indoline derivatives through mechanism resembling the carbon analogue of Norrish-Yang reaction. This process is facilitated by excited triplet-state carbon-centered biradicals, enabling 1,5-HAT suppressing critical 1,4-biradical intermediates from undergoing Norrish Type II cleavage reaction, pioneering unprecedented 1,6-HAT reactions initiated alkenes. We demonstrate synthetic utility compatibility method across various functional groups, validated scope evaluation, large-scale synthesis, derivatization. Our findings are supported control experiments, deuterium labeling, kinetic studies, cyclic voltammetry, Stern-Volmer density theory (DFT) calculations.

Language: Английский

Visible-Light-Mediated Energy Transfer Enables Cyclopropanes Bearing Contiguous All-Carbon Quaternary Centers DOI

Dingding Xia,

Rong-Kai Wu, Jinxin Wang

et al.

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(14), P. 9806 - 9816

Published: July 11, 2023

Cyclopropanes bearing contiguous all-carbon quaternary centers continue to attract attention due their bioactivities. However, methods obtain cyclopropanes with remain largely unexplored the high steric hindrance of these compounds. Herein, we report a visible-light-mediated energy-transfer (EnT) strategy realize in situ donor/donor carbenes from readily available N-tosylhydrazones, facilitating synthesis highly congested EWG-free cyclopropanes. Through this approach, are rapidly installed into complex bioactive molecules, fluorescent and other useful building blocks that challenging synthesize. Detailed mechanistic reactions DFT studies clearly demonstrated role photosensitizer, formation carbenes, necessity light base system.

Language: Английский

Citations

34
Exploration of Light Mediated Strategies in Four Membered Heterocycle Synthesis DOI
Suman Majee, Km. Anjali, Bimal Krishna Banik

et al.

Tetrahedron, Journal Year: 2025, Volume and Issue: unknown, P. 134493 - 134493

Published: Jan. 1, 2025

Language: Английский

Citations

1
Visible‐Light‐Mediated Energy Transfer Enables the Synthesis of β‐Lactams via Intramolecular Hydrogen Atom Transfer DOI Creative Commons

Meghan J. Oddy,

Daniel A. Kusza, Ryan G. Epton

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(48)

Published: Oct. 7, 2022

Abstract The synthesis of 2‐azetidinones (β‐lactams) from simple acrylamide starting materials by visible‐light‐mediated energy transfer catalysis is reported. reaction features a C(sp 3 )−H functionalization via variation the Norrish–Yang photocyclization involving carbon‐to‐carbon 1,5‐hydrogen atom (supported deuterium labelling and DFT calculations) can be used for construction diverse range β‐lactam products.

Language: Английский

Citations

30
Stereoselective synthesis of β-lactams: recent examples DOI Creative Commons
Adrián Saura-Sanmartín, Laura Andreu-Ardil

Organic & Biomolecular Chemistry, Journal Year: 2023, Volume and Issue: 21(16), P. 3296 - 3306

Published: Jan. 1, 2023

This review covers recent advances towards the stereoselective synthesis of β-lactam derivatives, which is a research topic great interest due to biological activity these molecules.

Language: Английский

Citations

13
Norrish-Yang-type cyclopropanation via functional group migration with photosensitizer at ppb loading DOI

Yingru Xu,

Jianjian Huang,

Tengfei Pang

et al.

Chem Catalysis, Journal Year: 2024, Volume and Issue: unknown, P. 101099 - 101099

Published: Sept. 1, 2024

Language: Английский

Citations

4
Successive energy-transfer catalytic dearomative reactions of quinolines with bicyclo[1.1.0]butanes for the synthesis of pyridine-fused 3D complicated molecules DOI Creative Commons
Cai Yiping, Shi Chen, Qin‐Hua Song

et al.

Organic Chemistry Frontiers, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

Successive energy-transfer-mediated dearomative [2π + 2σ] cycloaddition/1,6-HAT cascade reaction of quinolines with bicyclo[1.1.0]butanes provides a facile synthesis pyridine-fused 3D complicated molecules.

Language: Английский

Citations

0
Energy Transfer Catalysis Enabled 2,2,2‐Trifluoroethoxy‐Amination of Olefins DOI Creative Commons
Floriane Doche, Thibault Gallavardin, Thomas Poisson

et al.

ChemistryEurope, Journal Year: 2025, Volume and Issue: unknown

Published: May 6, 2025

A thioxanthone‐catalyzed 2,2,2‐trifluoroethoxyamination of olefins is developed via the formation corresponding alkoxy and iminyl radicals using unprecedented, easily prepared, bench‐stable oxime ethers as bifunctional reagents. To bypass possible side reactions (1,2‐Hydrogen Atom Transfer (HAT), H‐abstraction, β‐scission), high reactivity radical fine‐tuned to promote selective challenging a COCH 2 CF 3 bond. This reaction, involving triplet energy transfer process, allows concomitant CN COAlk bond, so far uncharted, ether Hence, difunctionalization myriad electron‐rich alkenes selectively afforded anti‐Markovnikov products with large functional group tolerance (44 examples, up 77% yield), offering straightforward complementary regioselectivity compared existing approaches for 2,2,2‐trifluoroethanol. Post‐functionalization mechanistic investigations provided key insights into reaction mechanism this transformation.

Language: Английский

Citations

0
Access to β‐Lactam Sulfonamides from Sulfamoyl Chlorides via Photoredox Catalyzed C−S Bond Formation DOI
Nejc Petek, Helena Brodnik, Uroš Grošelj

et al.

Advanced Synthesis & Catalysis, Journal Year: 2024, Volume and Issue: 366(15), P. 3310 - 3315

Published: June 13, 2024

Abstract Sulfonyl chlorides are a synthetically attractive source of sulfonyl radicals in photoredox catalysis and useful precursors the synthesis sulfones. Sulfamoyl chlorides, on other hand, remain poorly represented despite their similar potential. In this study, N ‐chlorosulfonylated β‐lactams were prepared from readily available utilized an atom transfer radical addition (ATRA) reaction with variety olefins, producing β‐lactam sulfonamides 49–95% yields. β‐Lactams fused to dihydro‐1,2‐thiazine ring which closely resemble carbacephems, widely used class antibiotics, also synthesized by intra‐molecular ATRA reaction. This methodology enables preparation sulfonamides, compounds that great interest pharmacology.

Language: Английский

Citations

3
Expanding the Chemical Space of Electrophilic β-Glycosyl β-Lactams through Photoinduced Diastereoselective Functionalization DOI Creative Commons
Éverton A. Tordato, Renan de Oliveira Gonçalves,

Lucas L. Baldassari

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(26), P. 5500 - 5505

Published: June 20, 2024

Herein, we present a photoinduced diastereoselective C-3 functionalization of electrophilic β-glycosyl β-lactams. The developed protocol is simple, mild, and scalable explores the use 3-exomethylene β-lactams as reaction partners in Giese type reaction. key nucleophilic alkyl radical generated by electron transfer process EDA complex formed NHPI Hantzsch esters. hydrogen atom to β-lactam intermediate enables synthesis various N-phenyl

Language: Английский

Citations

3
Visible Light Induced Difunctional Hetero‐Annulation of Unsaturated C−C Bonds DOI

Apurba Samanta,

Saradindu Debnath,

Partha Pratim Mondal

et al.

Advanced Synthesis & Catalysis, Journal Year: 2023, Volume and Issue: 365(19), P. 3182 - 3210

Published: Aug. 1, 2023

Abstract Heterocyclic scaffolds are beneficial structural architects in a wide range of pharmaceuticals, agrochemicals, biological and also functional materials. In this regard, several investigations have been performed to synthesize them. Among these, visible light‐induced difunctionalization cyclization strategy provides attractive solutions by adopting greener routes, breaking the monopoly conventional thermal processes. A review on these methodologies is desirable as unsaturated aliphatics, especially alkenes one cheapest feedstocks available. They offer diverse options modifications generate different products, including heterocycles, which highly sought after due their applications various sectors. To account for advancements strategy, we summarized light induced strategies that directly lead synthesis heterocyclic from C−C bonds. We categorized relevant reaction schemes into four mechanistically distinct sections namely (i) Two component oxidative annulations (ii) Radical mediated (iii) Polar radical crossover (iv) Three annulations.

Language: Английский

Citations

8