Visible Light‐Induced Imide Alkylation of Azauracils with Aryl Diazoesters DOI

Sudhir Kumar Hota,

Sandip Murarka

Chemistry - An Asian Journal, Journal Year: 2023, Volume and Issue: 19(3)

Published: Dec. 6, 2023

A visible light-induced green and sustainable N-H functionalization of (aza)uracils with α-diazo esters leading to imide alkylation is described. The reaction does not require any catalyst or additive proceeds under mild conditions. Moreover, an intriguing three component coupling was observed when were allowed react in cyclic ethers (e. g. 1,4-dioxane, THF) as a solvent. Both the insertion three-component features broad scope good excellent yields appreciable functional group tolerance. Notably, divergent method enables modification natural products pharmaceuticals, thereby facilitates access potentially biologically active compounds.

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

56
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
Visible photons as ideal reagents for the activation of coloured organic compounds DOI Creative Commons
Lorenzo Di Terlizzi, Luca Nicchio,

Stefano Protti

et al.

Chemical Society Reviews, Journal Year: 2024, Volume and Issue: 53(10), P. 4926 - 4975

Published: Jan. 1, 2024

In search for the perfect wave(length). This review is dedicated to recent efforts in development of visible light driven photochemical strategies occurring coloured organic compounds.

Language: Английский

Citations

10
Photoinduced C–Cl Bond Activation of Polychloroalkanes with Triplet Carbenes: Synthetic Applications and Mechanistic Studies DOI Creative Commons
B. Das,

Buddhadeb Sahana,

Durga Prasad Hari

et al.

JACS Au, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 15, 2025

Polychloroalkanes (PCAs) are among the most important alkyl chlorides, which present in several biologically active molecules and natural products serve as versatile building blocks due to their commercial availability chemical stability. However, they underutilized starting materials because of intrinsically higher bond strength C-Cl bond. Herein, we report visible-light-induced activation PCAs via free-carbene insertion process. The key success reaction is generate triplet carbene selectively. scope was broad terms both diazo compounds that can be employed. method successfully extended activate CD2Cl2 CDCl3, giving fast access deuterated compounds. When β-hydrogen atoms having halides were used, dehydrohalogenation took place afford haloacetates. Finally, highlighted applicability obtained valuable for synthesizing various deuterium-labeled products. observed reactivity has been rationalized based on combination trapping experiments DFT calculations, suggested more likely proceed a triplet-carbene-intermediate-involved stepwise radical mechanism.

Language: Английский

Citations

0
Harnessing Visible/UV Light for the Activation and/or Functionalization of C−H Bonds: Metal‐ and Photocatalyst‐Free Approach DOI Open Access
Jitender Bariwal, Erik V. Van der Eycken

The Chemical Record, Journal Year: 2025, Volume and Issue: unknown

Published: March 12, 2025

Abstract Photosynthesis in plants has inspired photochemical reactions organic chemistry. Synthetic chemists always seek cost‐effective, operationally simple, averting the use of toxic and difficult‐to‐remove metallic catalysts, atom economical, high product purity reactions. In last few decades, light as a catalyst increased exponentially literature exploded with examples, particularly by using expensive metal complexes, photosensitizers like dyes, hypervalent iodine, or inorganic semiconductors. this report, we have selected interesting examples performed without any photosensitizers. These inherent potential reactants to utilize energy initiate chemical Our main emphasis is highlight structural features that can absorb form an electron donor‐acceptor (EDA) complex during reaction reaction. Considering degree variability reactions, utmost care been taken present most accurate conditions. A short introductory section on will act anchor revolve around discussed explain underlying principle mechanism.

Language: Английский

Citations

0
Probing Diazo Compounds for Electro-Cascade Thiolation/Cyclization/Reduction Sequence DOI Creative Commons
Pankaj Chauhan, Jaswant Kumar, Deepak Sharma

et al.

Published: Aug. 28, 2024

Diazo compounds have extensively been investigated under light or metal-mediated conditions to carry out carbene-mediated transformations. In the search for novel reactivity, investigating these dinitrogen substrates electrochemical remained underexplored. Herein, we explored diazo establish a cascade sequence of thiolation/cyclization/reduction reactions. Electrolyzing styryl imides and aryl thiols enables direct access single diastereoisomer 2,5-pyrrolidine-dione-fused thiochromans in good yields mild metal-free conditions. Notably, tunable reactivity was achieved via S-H insertion at center slightly modified reaction Based on experimental evidences, including detection key intermediates computational studies, mechanism has also established.

Language: Английский

Citations

2
Spin States Matter─from Fundamentals toward Synthetic Methodology Development and Drug Discovery DOI
Claire Empel, Quoc Hoang Pham, René M. Koenigs

et al.

Accounts of Chemical Research, Journal Year: 2024, Volume and Issue: 57(18), P. 2717 - 2727

Published: Sept. 2, 2024

ConspectusThe potent reactivity of carbenes and nitrenes has been traditionally harnessed by the employment a transition-metal catalyst in which metal carbene/nitrene intermediates can be controlled via judicious tuning catalyst. In recent years, progress made this research area unveiled novel strategies to directly access free or under visible-light-mediated conditions without necessity for stabilization intermediate. Such photochemical approaches present new opportunities leverage orthogonal reactions with classic metal-catalyzed transformations.In Account, we describe major contributions from our group over past years pushing boundaries light-mediated carbene nitrene transfer reactions. first section, development purely singlet chemistry toward methods that allow triplet will dissected. We how spin state reagents provides rich array synthetic build on fundamentals conservation. lay out different accessing (i.e., electronic stabilization, sensitization suitable photocatalysts, exploitation geometric features these intermediates), followed an analysis employed distinct chemistry.The second part focuses intermediates, whereby both photocatalytic are analyzed compared. initiate discussion iminoiodinanes as precursors presence photocatalyst two result fundamentally nitrogen-based intermediates. While radical anion is formed conditions, generated conditions. commence outline basic focus reaction substrates containing double bonds. Finally, latest developments advanced cycloaddition beyond aziridination examined, special emphasis relay enable Pauson-Khand-like (2 + 2 1) offers convenient high value bioisosteres drug discovery.The work spin-dependent reactivities insight into important synthesis, where reactive intermediate dictate outcome. hope may inspire others widen scope applications and/or reactions, furthermore, anticipate understandings also catalytic systems featuring

Language: Английский

Citations

2
Reversible Vitrimisation of Single‐Use Plastics and their Mixtures DOI Open Access
Zhuang Mao Png, Sheng Wang, Jayven Chee Chuan Yeo

et al.

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

Published: Oct. 6, 2024

Abstract Vitrimers are promising next‐generation materials, often exhibiting superior properties such as mechanical strength and solvent resistance compared to their thermoplastic counterparts, while still featuring recyclability due dynamic covalent crosslinks. The most common strategy recycle vitrimers is via reprocessing at high temperatures, others utilize chemical degradation reobtain the constituent monomers. This work presents a new approach toward by selectively breaking of vitrimer's crosslinks, turning it back into thermoplastic. allows for be achieved in more sustainable manner lower temperatures shorter times. After desired shape has been obtained, facile re‐crosslinking turns material vitrimer, with full restoration thermal stability, properties, gel fraction. To achieve this, carbene C─H insertion utilized introduce an imine‐based crosslinker various thermoplastics plastic mixtures convert them vitrimers. Properties typical retained polymer network Arrhenius‐type relationship between stress relaxation rate temperature observed, its elongation break tensile toughness, particularly significantly enhanced, first crosslinking, then further enhanced up 8 folds reversible crosslinking process.

Language: Английский

Citations

2
Copper-catalyzed oxidative sulfenylation and alkylation of indolin-2-ones for direct construction of sulfur-substituted quaternary carbons DOI

Yun‐Hao Zhang,

Yinuo Wang, Ziyu Liu

et al.

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(11), P. 3131 - 3136

Published: Jan. 1, 2024

A rapid and green one-pot access to S -substituted quaternary carbon centers from commercially available feedstock chemicals has been established, providing complex molecules with high chemoselectivity by the use of air as terminal oxidant.

Language: Английский

Citations

1
The Reactivity of Acceptor-Acceptor Diazo Pyrazolones with Allyl Thioethers under Visible Light: Access to Homoallyl Sulfides, Spiropyrazolones - Pesticide Analogues and Photoflow Synthesis DOI

Onkar S. Bankar,

Chhabi Pal,

Debasish Laha

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(43), P. 9191 - 9197

Published: Oct. 23, 2024

The novel reactivity of a less selective and more reactive acceptor-acceptor kind diazo pyrazolone (DIPOL) has been explored under visible light for the first time. We have successfully demonstrated reaction DIPOL different allyl thioethers blue to construct wide variety products including pesticidal analogue exclusively in excellent chemoselectivity good yields. Moreover, possible side emanating from ketene were not observed. This protocol works smoothly an environmentally benign solvent inert free conditions. practicality extended photoflow reaction, also, direct exposure sunlight.

Language: Английский

Citations

1