Strained small rings in gold-catalyzed rapid chemical transformations

Lu, Beili; Dai, Lunzhi; Shi, Min

doi:10.1039/c2cs15295a

Cited by 228 publications

(94 citation statements)

References 212 publications

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“…Quantum chemical calculations show that the reaction is thermodynamically driven by the relief of ring strain from the cyclopropylidene moiety, and that the Au(I) catalyst greatly lowers the barrier for rearrangement. The type of strain relief described herein has potential as a general tool for the development of alternatives to otherwise unfavourable sigmatropic reactions 11,12 .…”

Section: Discussionmentioning

confidence: 99%

A gold-catalysed enantioselective Cope rearrangement of achiral 1,5-dienes

et al. 2012

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Since the discovery of the Cope rearrangement in the 1940s, no asymmetric variant of the rearrangement of achiral 1,5-dienes has emerged, despite the successes that have been achieved with its heteroatom variants (Claisen, aza-Cope, etc.). This article reports the first example of an enantioselective Cope reaction that starts from an achiral diene. The new gold(I) catalyst derived from double Cl−-abstraction of ((S)-3,5-xylyl-PHANEPHOS(AuCl)2), has been developed for the sigmatropic rearrangement of alkenyl-methylenecyclopropanes. The reaction proceeds at low temperature and the synthetically useful vinylcyclopropane products are obtained in high yield and enantioselectivity. Density functional theory calculations predict that: (1) the reaction proceeds via a cyclic carbenium ion intermediate, (2) the relief of strain in the methylenecyclopropane moiety provides the thermodynamic driving force for the rearrangement and (3) metal complexation of the transition-state structure lowers the rearrangement barriers.

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Section: Discussionmentioning

confidence: 99%

A gold-catalysed enantioselective Cope rearrangement of achiral 1,5-dienes

et al. 2012

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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

152

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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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“…The reasons are that the sizes calculated by Scherrer equation are just rough average values and have large error. And Scherrer equation has the detection limit of amount and particle size of the target crystallite material in mixed or composite materials [47][48][49]. When the size of nanocrystals exceeds a certain value, the intensity and of diffraction peak and the half-width values will not increase or decrease, respectively, at the corresponding magnification with increase of the size of nanocrystals.…”

Section: Synthesis and Characterization Of Hsns Carriersmentioning

confidence: 98%

Carrier effect in the synthesis of rattle-type Au@hollow silica nanospheres by impregnation and thermal decomposition method

2012

Microporous and Mesoporous Materials

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Strained small rings in gold-catalyzed rapid chemical transformations

Cited by 228 publications

References 212 publications

A gold-catalysed enantioselective Cope rearrangement of achiral 1,5-dienes

A gold-catalysed enantioselective Cope rearrangement of achiral 1,5-dienes

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

Carrier effect in the synthesis of rattle-type Au@hollow silica nanospheres by impregnation and thermal decomposition method

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