Organic Chemistry Frontiers, Journal Year: 2021, Volume and Issue: 8(21), P. 5982 - 5987
Published: Jan. 1, 2021
A green and efficient route for the synthesis of trisubstituted hydroxylamines from β-keto ester, 2-nitrosopyridine aryldiazoacetates has been reported. This multicomponent reaction occurred under mild conditions without catalysts or additives.
Language: Английский
Chemical Society Reviews, Journal Year: 2020, Volume and Issue: 49(19), P. 6833 - 6847
Published: Jan. 1, 2020
Carbenes are important intermediates in organic chemistry and have been widely applied various types of reactions, ranging from cycloaddition reactions sigmatropic rearrangements to C-H functionalizations, thus allowing the rapid construction densely functionalized molecules. Over past decades, remarkable progress has achieved metal-catalyzed carbene transfer reactions. Nevertheless, realizing these transformations under milder and/or greener conditions is still highly desirable. Only recently, visible light-promoted diazo compounds via free emerged as a practical, mild powerful tool. In this tutorial review, we summarize latest advances area, aiming at providing clear overview on reaction design, mechanistic scenarios potential future developments.
Language: Английский
Citations
350
Chemical Society Reviews, Journal Year: 2022, Volume and Issue: 51(6), P. 2145 - 2170
Published: Jan. 1, 2022
This review provides an overview of visible-light induced dearomatization reactions classified based on the manner in which aromaticity is disrupted.
Language: Английский
Citations
226
ACS Sustainable Chemistry & Engineering, Journal Year: 2021, Volume and Issue: 9(27), P. 8895 - 8918
Published: June 25, 2021
The development of new sustainable reactions and protocols is essential to fulfill the growing demands every branch organic chemistry for greener synthetic methodologies. In this context, use visible light as only source energy highly appealing. Since diazo compounds are valuable reagents in synthesis, their transformations realized a manner interest. High reactivity easy availability make them suitable solar-driven transformations. Indeed, photochemical have recently proven alternative transition metal catalysis. perspective, we highlight applications these under irradiation, particularly focusing on recent advancements. These include generation carbenes radicals which involve many relevant reactions, [2+1]-cycloadditions, X–H C–H insertions, Wolff rearrangement, more. Mechanistic aspects processes briefly addressed give readers deeper understanding rules underlying photoreactivity compounds. We conclude by emphasizing significant advancements discussing challenges future developments photochemistry reagents.
Language: Английский
Citations
177
Chemistry - A European Journal, Journal Year: 2020, Volume and Issue: 27(4), P. 1270 - 1281
Published: Aug. 5, 2020
Abstract Among the available methods to increase molecular complexity, sigmatropic rearrangements occupy a distinct position in organic synthesis. Despite being known for over century rearrangement reactions of ylides via carbene transfer reaction have only recently come age. Most ylide mediated processes involve rupture σ‐bond and formation new bond between π‐bond negatively charged atom followed by simultaneous redistribution π‐electrons. This minireview describes advances this research area made recent years, which now opens up metal‐catalyzed enantioselective reactions, metal‐free photochemical novel pathways that can be accessed intermediates.
Language: Английский
Citations
140
Chemical Communications, Journal Year: 2022, Volume and Issue: 58(17), P. 2788 - 2798
Published: Jan. 1, 2022
In this feature article, the photolysis and dye-sensitized reactions of diazoalkanes are discussed applications in organic synthesis presented.
Language: Английский
Citations
102
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
59
Chemical Communications, Journal Year: 2023, Volume and Issue: 59(48), P. 7346 - 7360
Published: Jan. 1, 2023
This article discusses the photochemistry of several diazo compounds undergoing visible light-mediated photolysis to generate free carbenes (or other highly reactive intermediates), which can be sequentially trapped by different reacting partners.
Language: Английский
Citations
46
Chem, Journal Year: 2020, Volume and Issue: 6(9), P. 2364 - 2381
Published: July 22, 2020
Lewis acidic boranes have been shown to be effective metal-free catalysts for highly selective reactions of donor-acceptor diazo compounds a range substrates. The α-aryl α-diazoesters with nitrogen heterocycles indole or pyrrole selectively generate C3 and C2 C–H insertion products, respectively, in good excellent yields even when using unprotected indoles. Alternatively, benzofuran, indene, alkene substrates give exclusively cyclopropanated products α-diazoesters, whereas the furans lead ring-opening. Comprehensive theoretical calculations used explain differing reactivities high selectivities these reactions. Overall, this work demonstrates catalytic (hetero)cycles alkenes. This simple, mild reaction protocol represents an alternative commonly precious metal systems may provide future applications generation biologically active compounds.
Language: Английский
Citations
82
Chemistry - A European Journal, Journal Year: 2019, Volume and Issue: 26(12), P. 2586 - 2591
Published: Dec. 11, 2019
The photolysis of diazoalkanes is a timely strategy to conduct carbene-transfer reactions under mild and metal-free reaction conditions, has developed as an important alternative conventional metal-catalyzed reactions. One the major limitations lies within rapidly occurring side carbene intermediate with remaining diazoalkane molecules that result in use excess partner thus impacts on efficiency. Herein, we describe protocol takes advantage situ generation donor-acceptor by Bamford-Stevens reaction. Following this strategy, concentration can be minimized reduce unwanted now photochemical transfer stoichiometric conditions. We have explored approach C-H N-H functionalization cyclopropanation N-heterocycles could demonstrate applicability method 51 examples.
Language: Английский
Citations
80
Journal of the American Chemical Society, Journal Year: 2020, Volume and Issue: 143(2), P. 604 - 611
Published: Dec. 31, 2020
Arene dearomatization is a straightforward method for converting an aromatic feedstock into functionalized carbocycles. Enantioselective dearomatizations of chemically inert arenes, however, are quite limited and underexplored relative to those phenols indoles. We developed diazo-free generation silver-carbene species from ynamide applied it the nonactivated arenes. Transiently generated norcaradiene could be trapped by intermolecular [4 + 2] cycloaddition, synthesizing polycycles with five consecutive stereogenic centers. This protocol constitutes first highly enantioselective reaction based on species. Mechanistic investigations revealed followed two different classes pericyclic reactions, as well origin chemo- enantioselectivity.
Language: Английский
Citations
76