Recent Advances in the Cycloisomerizations of Methylenecyclopropanes using Gold Catalysis

Fang, Wei; Shi, Min

doi:10.1002/chem.201705788

Cited by 36 publications

(18 citation statements)

References 76 publications

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“…Homogenous gold catalytic transformations have witnessed significant development during the past decade. These catalytic processes have been popularized as methods to rapidly construct complex and distinct molecular structures in methodology studies and natural product synthesis. − The important and unique character of the gold catalytic process is the ability of the catalyst to selectively activate π-rich systems, thereby enabling active activation of alkynes, alkenes, and allenes that are tethered or conjugated with strained small ring systems such as methylenecyclopropanes (MCPs), vinylidenecyclopropanes (VDCPs), cyclopropenes, aziridines, and epoxides. − Furthermore, owing to the single bond in the strained carbo- and heterocyclic ring having a partial π-character, the strained ring system itself, is also a suitable point of activation for gold catalytic transformations (Scheme ). Finally, in strained ring-systems, such as epoxides and aziridines, the gold catalyst can also activate the substrate through binding to the lone-pair of the heteroatom.…”

Section: Introductionmentioning

confidence: 99%

“…In recent years, several major reviews − ,− , on gold-catalyzed conversion of highly strained compounds and the applications of these processes have been published. However, there has been significant activity in the development of novel transformations of strained small rings upon gold catalysis in recent years, making a comprehensive review on the topic timely.…”

Section: Introductionmentioning

confidence: 99%

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Gold-Catalyzed Conversion of Highly Strained Compounds

et al. 2020

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The past decade has witnessed the golden age of homogeneous gold-catalyzed reactions, especially those that involve the transformation of highly strained molecules into complex molecular architectures. Gold catalysts, with unique electronic properties and catalytic abilities, have elevated versatile reaction modes through π-interaction induced activation. On the basis of increasing research interest in this topic, together with the significant development of various ligands, including phosphine ligands and azacyclic or noncyclic carbene ligands, the understanding of the catalytic function of gold catalysts has become much deeper and more comprehensive. Different reaction needs thus could be adapted by a novel gold catalyst with a diversified ligand selection. Furthermore, the whole evolution of the gold catalysis on synthetic methodologies has realized and expanded its application into natural product synthesis as well as the potentiality of drug discovery, which endows this ancient metal with a magnificent renaissance. The reactivity of strained small ring molecules with high tension has always been an important research topic in organic chemistry. When the highly strained small ring is linked with a π-electron rich moiety or contains a heteroatom, the gold activation of the π-system or coordination with the heteroatom can initiate a cascade reaction, usually followed by ring opening or expansion. These processes can result in the rapid construction of complex and distinct molecular structures, many of which feature in biologically important molecules. In this review, we will mainly summarize the advances on diverse reaction types and molecular constructions accomplished by homogeneous gold catalysis using highly strained substrates, including methylenecyclopropanes (MCPs), vinylidenecyclopropanes (VDCPs), cyclopropenes as well as aziridine- and epoxide-containing molecules, focusing on the last 10 years. For functionalized alkynyl cyclopropanes, several early inspiring and elegant examples will be described in this review for systematically understanding these transformations.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Gold-Catalyzed Conversion of Highly Strained Compounds

et al. 2020

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“…[11,12,[32][33][34][35][36][37][38][39] Sub-nanometer-sized unsupported gold clusters can accelerate specific reactions with extremely large turnover numbers( TONs) and turnover frequencies (TOFs). [69,70,[79][80][81][82][71][72][73][74][75][76][77][78] In the majority of homogeneous Au catalysts, Au exists in the + 1 oxidation state. [43][44][45] Owing to the localizeds urface plasmon resonance (LSPR)e ffects, [46][47][48] gold nanoparticles (AuNPs) can be used as photocatalysts.…”

Section: Introductionmentioning

confidence: 99%

Gold‐Catalyzed Cross‐Coupling Reactions: An Overview of Design Strategies, Mechanistic Studies, and Applications

Nijamudheen

Datta

2019

Chemistry A European J

153

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Transition-metal-catalyzed cross-couplingr eactions are central to many organic synthesis methodologies. Traditionally,P d, Ni, Cu, and Fe catalysts are used to promote these reactions. Recently,m any studies have showedt hat both homogeneous and heterogeneous Au catalysts can be used for activating selective cross-coupling reactions.H ere, an overview of the past studies, current trends, andf uture directions in the field of gold-catalyzed coupling reactions is presented.D esign strategiest oa ccomplish selective homocoupling and cross-coupling reactions under both homogeneous and heterogeneous conditions, computational and ex-perimental mechanistic studies, and their applicationsi nd iverse fields are critically reviewed. Specific topics covered are:o xidant-assisted and oxidant-free reactions;s train-assisted reactions;d ual Au and photoredoxc atalysis;b imetallic synergistic reactions;m echanismso fr eductivee limination processes;e nzyme-mimicking Au chemistry;c lustera nd surface reactions;a nd plasmonic catalysis. In the relevant sections, theoretical and computational studies of Au I /Au III chemistry are discussed and the predictionsf rom the calculationsa re compared with the experimental observations to derive useful design strategies.A. Nijamudheen earnedh is PhD from IACS, Kolkata,i n2 015. Currently,h ei sapostdoctoral researcher atF loridaS tate University.H is researchi nterests are in computational catalysis, solar energym aterials, and beyond Li-ion battery technologies.Ayan Dattai sc urrently aP rofessor at IACS, Kolkata.H is research interests include theoretical and computational studieso ft ransitionmetal-catalyzed reactions,o pto-electronic properties of organic and solid-statem aterials, and the design of renewableenergymaterials. He has won several awards including the DST-SERB Distinguished Investigator Award (DIA) in 2019.

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Section: Construction Of 4-membered Rings Catalyzed By Goldmentioning

confidence: 99%

“…699 However, these were isolated examples, and in most of the cases, the gold(I)-catalyzed [2 + 2] cycloaddition of 1,6-enynes competes with other skeletal rearrangements, which prevent the selective formation of cyclobutenes (Scheme 142B). 643,699,700 The ligand employed was found to affect the regioselectivity of these transformations. 699 Regarding the mechanism for the formation of cyclobutenes, computational studies revealed that the most favorable pathway begins with a 6-endo-dig cyclization to form cyclopropyl gold(I) carbene 657 (Scheme 143A).…”

Section: Synthesis Of Cyclobutanesmentioning

confidence: 99%

Gold-Catalyzed Synthesis of Small Rings

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Three- and four-membered rings, widespread motifs in nature and medicinal chemistry, have fascinated chemists ever since their discovery. However, due to energetic considerations, small rings are often difficult to assemble. In this regard, homogeneous gold catalysis has emerged as a powerful tool to construct these highly strained carbocycles. This review aims to provide a comprehensive summary of all the major advances and discoveries made in the gold-catalyzed synthesis of cyclopropanes, cyclopropenes, cyclobutanes, cyclobutenes, and their corresponding heterocyclic or heterosubstituted analogs.

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Recent Advances in the Cycloisomerizations of Methylenecyclopropanes using Gold Catalysis

Cited by 36 publications

References 76 publications

Gold-Catalyzed Conversion of Highly Strained Compounds

Gold-Catalyzed Conversion of Highly Strained Compounds

Gold‐Catalyzed Cross‐Coupling Reactions: An Overview of Design Strategies, Mechanistic Studies, and Applications

Gold-Catalyzed Synthesis of Small Rings

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