Synthesis of Medium-Sized Heterocycles by Transition-Metal-Catalyzed Intramolecular Cyclization DOI Creative Commons

Mickaël Choury,

Alexandra Basilio Lopes,

Gaëlle Blond

et al.

Molecules, Journal Year: 2020, Volume and Issue: 25(14), P. 3147 - 3147

Published: July 9, 2020

Medium-sized heterocycles (with 8 to 11 atoms) constitute important structural components of several biologically active natural compounds and represent promising scaffolds in medicinal chemistry. However, they are under-represented the screening chemical libraries as a consequence being difficult access. In particular, methods involving intramolecular bond formation challenging due unfavorable enthalpic entropic factors, such transannular interactions conformational constraints. The present review focuses on synthesis medium-sized by transition-metal-catalyzed cyclization, which despite its drawbacks remains straightforward attractive strategy. obtained differ their nature, number heteroatoms, ring size. classified according metal used (palladium, copper, gold, silver), then subdivided type formed, namely carbon-carbon or carbon-heteroatom.

Language: Английский

Visible Light-Induced Transition Metal Catalysis DOI
Kelvin Pak Shing Cheung, Sumon Sarkar, Vladimir Gevorgyan

et al.

Chemical Reviews, Journal Year: 2021, Volume and Issue: 122(2), P. 1543 - 1625

Published: Oct. 8, 2021

In recent years, visible light-induced transition metal catalysis has emerged as a new paradigm in organic photocatalysis, which led to the discovery of unprecedented transformations well improvement known reactions. this subfield complex serves double duty by harvesting photon energy and then enabling bond forming/breaking events mostly via single catalytic cycle, thus contrasting established dual photocatalysis an exogenous photosensitizer is employed. addition, approach often synergistically combines catalyst–substrate interaction with photoinduced process, feature that uncommon conventional photoredox chemistry. This Review describes early development advances emerging field.

Language: Английский

Citations

549
Skeletal editing through direct nitrogen deletion of secondary amines DOI
Sean H. Kennedy, Balu D. Dherange, Kathleen J. Berger

et al.

Nature, Journal Year: 2021, Volume and Issue: 593(7858), P. 223 - 227

Published: May 12, 2021

Language: Английский

Citations

242
Construction of Medium-Sized Rings by Gold Catalysis DOI
Ronald L. Reyes, Tomohiro Iwai, Masaya Sawamura

et al.

Chemical Reviews, Journal Year: 2020, Volume and Issue: 121(14), P. 8926 - 8947

Published: Oct. 6, 2020

Compounds having cyclic molecular frameworks are highly regarded for their abundance and diverse utilities. In particular, medium-sized carbocycles heterocycles exist in a broad spectrum of natural products, bioactive therapeutics, medicinally significant synthetic molecules. Metal-mediated methods have been developed the preparation compounds containing ring (MSR) through cyclization different classes substrates acyclic precursors. This review focuses on methodologies construction MSRs via gold catalysis. Given challenges enabling assembly sizes, we present here accounts Au-mediated giving notable 7-membered (8–11-membered ring) structures. Emphasis pathway mode selection precursors ranging from structurally biased were outlined. Reactivity patterns choice efficient Au catalysts controlling reaction performance selectivity addition to mechanistic attributes examined.

Language: Английский

Citations

183
Carbon Atom Insertion into Pyrroles and Indoles Promoted by Chlorodiazirines DOI Creative Commons
Balu D. Dherange, Patrick Q Kelly, Jordan P. Liles

et al.

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(30), P. 11337 - 11344

Published: July 21, 2021

Herein, we report a reaction that selectively generates 3-arylpyridine and quinoline motifs by inserting aryl carbynyl cation equivalents into pyrrole indole cores, respectively. By employing α-chlorodiazirines as thermal precursors to the corresponding chlorocarbenes, traditional haloform-based protocol central parent Ciamician-Dennstedt rearrangement can be modified directly afford 3-(hetero)arylpyridines quinolines. Chlorodiazirines are conveniently prepared in single step oxidation of commercially available amidinium salts. Selectivity function substitution pattern was examined, predictive model based on steric effects is put forward, with DFT calculations supporting selectivity-determining cyclopropanation step. Computations surprisingly indicate stereochemistry little consequence subsequent electrocyclic ring opening forges pyridine core, due compensatory homoaromatic stabilization counterbalances orbital-controlled torquoselectivity effects. The utility this skeletal transform further demonstrated through preparation quinolinophanes editing pharmaceutically relevant pyrroles.

Language: Английский

Citations

179
A happy medium: the synthesis of medicinally important medium-sized rings via ring expansion DOI Creative Commons

Aimee K. Clarke,

William P. Unsworth

Chemical Science, Journal Year: 2020, Volume and Issue: 11(11), P. 2876 - 2881

Published: Jan. 1, 2020

Medium-sized rings have much promise in medicinal chemistry, but are difficult to make using direct cyclisation methods. In this minireview, we highlight the value of ring expansion strategies address long-standing synthetic challenge. We drawn on recent progress (post 2013) key reaction design features that enable successful 'normal-to-medium' for synthesis these medicinally important molecular frameworks, currently under-represented compound screening collections and marketed drugs view their challenging syntheses.

Language: Английский

Citations

171
Phosphoranyl Radical Fragmentation Reactions Driven by Photoredox Catalysis DOI Creative Commons
James A. Rossi‐Ashton,

Aimee K. Clarke,

William P. Unsworth

et al.

ACS Catalysis, Journal Year: 2020, Volume and Issue: 10(13), P. 7250 - 7261

Published: June 5, 2020

Photocatalytic generation of phosphoranyl radicals is fast emerging as an essential method for the diverse and valuable radicals, typically via deoxygenation or desulfurization processes. This Perspective a comprehensive evaluation all studies using tunable mediators in photoredox catalysis, highlighting how two distinct methods radical formation (radical addition nucleophilic addition) can be used to generate versatile intermediates with reactivity profiles.

Language: Английский

Citations

157
Dearomative ring expansion of thiophenes by bicyclobutane insertion DOI
Huamin Wang, Huiling Shao, Ankita Das

et al.

Science, Journal Year: 2023, Volume and Issue: 381(6653), P. 75 - 81

Published: July 6, 2023

Skeletal ring enlargement is gaining renewed interest in synthetic chemistry and has recently focused on insertion of one or two atoms. Strategies for heterocyclic expansion through small-ring remain elusive, although they would lead to the efficient formation bicyclic products. Here, we report a photoinduced dearomative thiophenes by bicyclo[1.1.0]butanes produce eight-membered rings under mild conditions. The value, broad functional-group compatibility, excellent chemo- regioselectivity were demonstrated scope evaluation product derivatization. Experimental computational studies point toward photoredox-induced radical pathway.

Language: Английский

Citations

115
Skeletal Editing of (Hetero)Arenes Using Carbenes DOI
Zhaohong Liu, Paramasivam Sivaguru, Yongquan Ning

et al.

Chemistry - A European Journal, Journal Year: 2023, Volume and Issue: 29(42)

Published: May 26, 2023

Abstract (Hetero)arenes continue to prove their indispensability in pharmaceuticals, materials science, and synthetic chemistry. As such, the controllable modification of biologically significant (hetero)arenes towards diverse more‐potent complex molecular scaffolds through peripheral skeletal editing has been considered a challenging goal organic Despite many excellent reviews on ( i. e ., C−H functionalization) (hetero)arenes, editings via single atom insertion, deletion, or transmutations have received less attention review literature. In this review, we systematically summarize state‐of‐the‐art reactions using carbenes, with focus general mechanistic considerations applications natural product syntheses. The potential opportunities inherent challenges encountered while developing these strategies are also highlighted.

Language: Английский

Citations

75
Enantioselective Synthesis of Chiral Medium-Sized Cyclic Compounds via Tandem Cycloaddition/Cope Rearrangement Strategy DOI
Xing Gao, Miaoren Xia, Chunhao Yuan

et al.

ACS Catalysis, Journal Year: 2019, Volume and Issue: 9(3), P. 1645 - 1654

Published: Jan. 11, 2019

The nine-membered ring-bearing bicyclo[5.2.2]tetrahydrooxonines frameworks have enantioselectively been constructed via a tandem [3 + 2] cycloaddition/Cope rearrangement reaction of vinylethylene carbonates (VECs) with coumalates or pyrones. Under mild conditions, palladium-catalyzed asymmetric various substituted VECs and pyrones proceeds smoothly to produce the corresponding medium-sized heterocyclic compounds in high yields very enantioselectivities. Moreover, on gram scale further diverse transformations products were workable. mechanism was investigated through control experiments DFT calculations, which show pathway rather than [5 4] cycloaddition pathway.

Language: Английский

Citations

123
Direct Photocatalytic Synthesis of Medium‐Sized Lactams by C−C Bond Cleavage DOI
Na Wang, Qiang‐Shuai Gu, Zhong‐Liang Li

et al.

Angewandte Chemie International Edition, Journal Year: 2018, Volume and Issue: 57(43), P. 14225 - 14229

Published: Sept. 4, 2018

Reported is a novel two-step ring-expansion strategy for expeditious synthesis of all ring sizes synthetically challenging (hetero)aryl-fused medium-sized lactams from readily available 5-8-membered cyclic ketones. This step-economic approach features remote radical (hetero)aryl migration C to N under visible-light conditions. Broad substrate scope, good functional-group tolerance, high efficiency, and mild reaction conditions make this procedure very attractive. In addition, method also provides expedient access 13-15-membered macrolactams upon an additional one-step manipulation. Mechanistic studies indicate that the involves amidyl promoted by acid.

Language: Английский

Citations

114