Photosensitizer-free visible light-mediated gold-catalysed cis-difunctionalization of silyl-substituted alkynes

Deng, Jie‐Ren; Chan, Wing Cheung; Lai, Nien-Chu; Yang, Bin; Tsang, Chui Shan; Ko, Ben C.B.; Chan, S. C.; Wong, Man Leung

doi:10.1039/c7sc02294h

Cited by 61 publications

(61 citation statements)

References 67 publications

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“…[289] The reaction is chemoand regioselective toward cis-substituted products rather than the more common trans-isomers. [289] The reaction is chemoand regioselective toward cis-substituted products rather than the more common trans-isomers.…”

Section: Dual Gold and Photoredox Catalysisf Or Cross-couplingr Eactionsmentioning

confidence: 99%

“…Controlled experiments, DFT calculations,a nd NMR and ESI-MS spectroscopic studies revealed that the reaction is initiated by as ingle-electron transfer (SET) at Au I .T he photoactivationo fa ryl diazonium salts will be followed by the addition of the in situ generated aryl radicalt ot he Au II intermediate, which would produce an Au III intermediate. (a) Photocatalyst-freed ualAua nd visible-light-promoted syn-difunctionalization of alkynes and (b) plausible mechanisms proposed by Deng et al [289] Scheme58. Finally,a facile reductive elimination process would lead to the crosscoupledp roduct.…”

Section: Dual Gold and Photoredox Catalysisf Or Cross-couplingr Eactionsmentioning

confidence: 99%

“…[292] They have demonstrated that under visible-light activation, oxidative addition of alkynyl iodide to Au I through an energy transfer mechanism can furnishC (sp 2 )ÀC(sp) crosscoupling reactions at room temperature. Specifically, they studied the visible-light-assisted synthesis of al- [289] Scheme58. (a) Dual Au and visible-light-promoted Suzuki coupling reaction for the selective synthesis of hetero-biaryls.…”

Section: Dual Gold and Photoredox Catalysisf Or Cross-couplingr Eactionsmentioning

confidence: 99%

“…Deng et al. later reported a photocatalyst‐free, Au‐ and visible‐light‐mediated route for the cis‐ difunctionalization of silyl‐substituted alkynes (Scheme ) . The reaction is chemo‐ and regioselective toward cis‐ substituted products rather than the more common trans‐ isomers.…”

Section: Dual Gold and Photoredox Catalysis For Cross‐coupling Reactionsmentioning

confidence: 99%

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

Nijamudheen

Datta

2019

Chemistry A European J

145

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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: Dual Gold and Photoredox Catalysisf Or Cross-couplingr Eactionsmentioning

confidence: 99%

Section: Dual Gold and Photoredox Catalysisf Or Cross-couplingr Eactionsmentioning

confidence: 99%

Section: Dual Gold and Photoredox Catalysisf Or Cross-couplingr Eactionsmentioning

confidence: 99%

Section: Dual Gold and Photoredox Catalysis For Cross‐coupling Reactionsmentioning

confidence: 99%

See 2 more Smart Citations

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

Nijamudheen

Datta

2019

Chemistry A European J

145

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“…[46] In 2017, the group of Wong used Ph 3 PAuCl as ac atalystt o describe an interesting cis-difunctionalizationo fs ilyl-substituted alkynes, which delivered silyl-substituted quinolizinium compounds under blue LEDs irradiation (Scheme 18 a). [47] Notably,t he reaction involved an unusual syn insertion and proceeded with high chemo-and regioselectivity.T he mechanism was studied by NMR spectroscopy,E SI-MS, and UV/Vis absorption. It wasf ound that whereas Ph 3 PAuCl did not absorb at l abs > 395 nm, the aryl diazonium salt presentedatail of the lowest energy absorption peak at l abs > 395 nm.…”

Section: Gold(i) Oxidation With Aryldiazonium Salts Assisted By Lightmentioning

confidence: 99%

Insights into the Mechanism of Gold(I) Oxidation with Aryldiazonium Salts

Medina‐Mercado

Porcel

2020

Chemistry A European J

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In the last decade, aryldiazoniums alts have attracted interest as coupling partnersi nc ross-couplingr eactions mediated by gold. Initially,t he presence of ap hotocatalyst and al ight sourcew as neededt oa chieve gold oxidation with these electrophiles.H owever, recently,i th as been shown that in some instances just heating, light irradiation, or the addition of certain bases and/or nucleophiles is enough. In this review,t he transformations developed so far using aryldiazonium salts as electrophiles are summarized with special emphasis on mechanistic studies.T he information gained by different authors, indicatest hat the specific steps of gold oxidation with aryldiazonium salts depends upon the activation mode of the diazonium salt.

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A Radical Chain: Mononuclear “Gold Only” Photocatalysis

et al. 2021

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We herein report an unprecedented reactivity of mononuclear gold catalysts acting as classical catalysts and at the same time as active partners in a radical chain mechanism, whereby gold is the only catalyst. The mechanism of the photo‐induced photosensitizer‐free “gold only”‐catalyzed cross coupling was studied in detail – experimentally and theoretically – based on the reaction between arylboronic acids and aryldiazonium salts. With a systematic set of stoichiometric experiments under various conditions and analytic methods, we could show that this mechanism is initiated by an aryl radical formed in the presence of blue LEDs and MeOH. This aryl radical enters the catalytic cycle to oxidize gold(I) to gold(II). Single electron transfer from gold(II) to the aryldiazonium salt then gives the cationic gold(III) complex by formation of a chain‐supporting aryl radical which then is enabled to start a new cycle by oxidation of gold(I) without the need for irradiation. At least every 432 cycles of the radical chain, a new chain‐initiating radical has to restart the radical chain. Eventually, the boronic acid is activated by the BF4− anion to transmetalate to gold(III), and reductive elimination delivers the desired product.

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Photosensitizer-free visible light-mediated gold-catalysed cis-difunctionalization of silyl-substituted alkynes

Abstract: A new photosensitizer-free visible light-mediated gold-catalysed cis-difunctionalization reaction is developed.

Cited by 61 publications

References 67 publications

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

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

Insights into the Mechanism of Gold(I) Oxidation with Aryldiazonium Salts

A Radical Chain: Mononuclear “Gold Only” Photocatalysis

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