Gold-Catalyzed Oxidative Cross-Coupling of Terminal Alkynes: Selective Synthesis of Unsymmetrical 1,3-Diynes

Peng, Haihui; Xi, Yumeng; Ronaghi, Nima; Dong, Boliang; Akhmedov, Novruz G.; Shi, Xiaodong

doi:10.1021/ja5078365

Cited by 175 publications

(102 citation statements)

References 46 publications

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“…Furthermore, Phen ligand is crucial to stabilize the Au(III) intermediate and presumably has a significant influence on the rate of reductive elimination as suggested in our previous work (entry 9). 37 Notably, under typical copper-promoted Glaser or Hay conditions, less than 15% yield of product was obtained with low conversion. Under the bi-phase conditions reported by Collins’ group, a lower yield was obtained.…”

Section: Resultsmentioning

confidence: 99%

Gold-Catalyzed Oxidative Coupling of Alkynes toward the Synthesis of Cyclic Conjugated Diynes

Peng

Wei

et al. 2018

Chem

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A gold-catalyzed oxidative coupling of alkynes was developed as an efficient approach for the synthesis of challenging cyclic conjugated diynes (CCD). Compared to the classical copper-promoted oxidative coupling reaction of alkynes, this gold-catalyzed process exhibits a faster reaction rate due to the rapid reductive elimination from the Au(III) intermediate. This unique reactivity thus allowed a challenging diyne macrocyclization to take place in high efficiency. Condition screening revealed a [(n-Bu)4N]+[Cl-Au-Cl]− salt as the optimal pre-catalyst. Macrocycles with ring size between 13 to 28 atoms were prepared in moderate to good yields, which highlighted the broad substrate scope of this new strategy. Furthermore, the synthetic utilities of the cyclic conjugated diynes for copper-free click chemistry have been demonstrated, which showcased the potential application of this strategy in biological systems.

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Section: Resultsmentioning

confidence: 99%

Gold-Catalyzed Oxidative Coupling of Alkynes toward the Synthesis of Cyclic Conjugated Diynes

Peng

Wei

et al. 2018

Chem

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“…[199] They reported selective cross-coupling reactions of the alkyne partners. [199] They reported selective cross-coupling reactions of the alkyne partners.…”

Section: Hypervalent Iodine As the Oxidant For Mediating Au I / Au Iimentioning

confidence: 99%

“…[201] The use of the Ph 3 PAuCl complex with PhI(OAc) 2 andN aHCO 3 led to optimum reaction conditions. Proposed mechanisms for the hypervalenti odine and Au catalyzed,oxidative cross-coupling of (a) terminalalkynes [199] and(b) unactivated arenes. Representative examples for homogeneousAu-catalyzed oxidativecrosscoupling of areneswith (a) stronglyelectron-deficient aryl boranes [196] and (b) aryl germanes.…”

Section: Hypervalent Iodine As the Oxidant For Mediating Au I / Au Iimentioning

confidence: 99%

“…[199] In such cases, the selectives ynthesis of unsymmetrical 1,3-diynes can be achieved by starting from at er-minal alkyne and an alkynyl hypervalent iodine reagent (Scheme 27). [199] In such cases, the selectives ynthesis of unsymmetrical 1,3-diynes can be achieved by starting from at er-minal alkyne and an alkynyl hypervalent iodine reagent (Scheme 27).…”

Section: Hypervalent Iodine As the Oxidant For Mediating Au I / Au Iimentioning

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

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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“…[7] With the aid of as trong oxidant (PIDA) and phenanthroline ligand, rapid reductive elimination of the Au III intermediate led to facile and selective diyne formation. [7] With the aid of as trong oxidant (PIDA) and phenanthroline ligand, rapid reductive elimination of the Au III intermediate led to facile and selective diyne formation.…”

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confidence: 99%

Ligand‐Assisted Gold‐Catalyzed Cross‐Coupling with Aryldiazonium Salts: Redox Gold Catalysis without an External Oxidant

et al. 2015

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Gold-catalyzed C(sp)-C(sp(2)) and C(sp(2))-C(sp(2)) cross-coupling reactions are accomplished with aryldiazonium salts as the coupling partner. With the assistance of bpy ligand, gold(I) species were oxidized to gold(III) by diazonium without any external oxidants. Monitoring the reaction with NMR and ESI-MS provided strong evidence for the nitrogen extrusion followed by Au(III) reductive elimination as the key step.

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Gold-Catalyzed Oxidative Cross-Coupling of Terminal Alkynes: Selective Synthesis of Unsymmetrical 1,3-Diynes

Cited by 175 publications

References 46 publications

Gold-Catalyzed Oxidative Coupling of Alkynes toward the Synthesis of Cyclic Conjugated Diynes

Gold-Catalyzed Oxidative Coupling of Alkynes toward the Synthesis of Cyclic Conjugated Diynes

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

Ligand‐Assisted Gold‐Catalyzed Cross‐Coupling with Aryldiazonium Salts: Redox Gold Catalysis without an External Oxidant

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