Subtopic Deep Dive
Gold π-Acid Catalyzed Alkyne Activation
Research Guide
What is Gold π-Acid Catalyzed Alkyne Activation?
Gold π-acid catalyzed alkyne activation employs gold(I) complexes as carbophilic Lewis acids to coordinate alkyne π-bonds, facilitating nucleophilic additions and skeletal rearrangements via slipped carbocation intermediates.
This subtopic centers on gold's activation of alkynes for reactions like hydroamination and cycloisomerizations, characterized by intermediates probed via spectroscopy and DFT. Foundational work by Tiekink et al. (2013) highlights gold-π interactions in catalysis (42 citations). Key studies include mechanistic insights from Kumar (2014) and Wang (2012) on nucleophilic additions to allenes and alkynes.
Why It Matters
Gold π-acid catalysis enables selective transformations of alkynes into complex heterocycles and natural products, impacting pharmaceutical synthesis. Tiekink et al. (2013) document the exponential rise in gold catalysis publications, driving efficient C-C and C-N bond formations (42 citations). Kumar (2014) provides mechanistic details for designing ligand-tuned gold catalysts, while Wang (2012) demonstrates enantioselective additions, guiding scalable processes in organic synthesis.
Key Research Challenges
Slipped Carbocation Intermediates
Characterizing transient gold-alkyne slipped carbocations remains difficult despite DFT and spectroscopic efforts. Kumar (2014) notes unresolved pathways in gold catalysis mechanisms. Experimental validation lags behind computations.
Ligand Effects on Selectivity
Tuning phosphine ligands for regioselective alkyne activation challenges catalyst design. Wang (2012) explores gold(I)-mediated additions but highlights substrate-dependent outcomes. Predictive models for ligand performance are limited.
Catalyst Deactivation Pathways
Gold catalyst poisoning by nucleophiles or aggregates reduces reaction efficiency. Tiekink et al. (2013) discuss supra-molecular gold-π interactions potentially leading to aggregation. Recycling strategies remain underdeveloped.
Essential Papers
Palladium and Copper Catalyzed Sonogashira cross Coupling an Excellent Methodology for C-C Bond Formation over 17 Years: A Review
Iram Kanwal, Aqsa Mujahid, Nasır Rasool et al. · 2020 · Catalysts · 142 citations
Sonogashira coupling involves coupling of vinyl/aryl halides with terminal acetylenes catalyzed by transition metals, especially palladium and copper. This is a well known reaction in organic synth...
Allenes, versatile unsaturated motifs in transition-metal-catalysed [2+2+2] cycloaddition reactions
Agustí Lledó, Anna Pla‐Quintana, Anna Roglans · 2016 · Chemical Society Reviews · 140 citations
This<italic>Tutorial Review</italic>highlights the versatility of allenes as unsaturated substrates in transition-metal-catalysed [2+2+2] cycloaddition reactions in generating complex architectures.
Scope and advances in the catalytic propargylic substitution reaction
Rashmi Roy, Satyajit Saha · 2018 · RSC Advances · 132 citations
Direct nucleophilic displacement of the alpha-hydroxy of the propargylic alcohol is one of the sought-after methods in the current scenario. An updated summary of the recent developments in this fi...
Computational ligand design in enantio- and diastereoselective ynamide [5+2] cycloisomerization
Robert N. Straker, Qian Peng, Aroonroj Mekareeya et al. · 2016 · Nature Communications · 123 citations
Generation of Axially Chiral Fluoroallenes through a Copper-Catalyzed Enantioselective β-Fluoride Elimination
Thomas J. O’Connor, Binh Khanh, Jordan Nafie et al. · 2021 · Journal of the American Chemical Society · 70 citations
Herein we report the copper-catalyzed silylation of propargylic difluorides to generate axially chiral, tetrasubstituted monofluoroallenes in both good yields (27 examples >80%) and enantioselectiv...
A ligand-directed divergent catalytic approach to establish structural and functional scaffold diversity
Yen‐Chun Lee, Sumersing Patil, Christopher Golz et al. · 2017 · Nature Communications · 66 citations
Photoinduced ynamide structural reshuffling and functionalization
Mohana Reddy Mutra, Jeh‐Jeng Wang · 2022 · Nature Communications · 46 citations
Reading Guide
Foundational Papers
Start with Tiekink et al. (2013, 42 citations) for gold-π catalysis overview, then Wang (2012) for Au(I)-allene additions, and Kumar (2014) for alkyne mechanistic insights.
Recent Advances
Study Goodman et al. (2019, 44 citations) for metal-stabilized carbocations relevant to gold intermediates.
Core Methods
Core techniques: Au(PPh3)+ coordination, NMR/IRI spectroscopy for intermediates, DFT for transition states (Kumar 2014; Tiekink 2013).
How PapersFlow Helps You Research Gold π-Acid Catalyzed Alkyne Activation
Discover & Search
Research Agent uses searchPapers and citationGraph on 'gold π-acid alkyne' to map 250M+ papers, revealing Tiekink et al. (2013) as a foundational node (42 citations) with links to Kumar (2014). exaSearch uncovers related mechanistic studies, while findSimilarPapers expands to Wang (2012) for nucleophilic additions.
Analyze & Verify
Analysis Agent applies readPaperContent to extract intermediates from Kumar (2014), then verifyResponse with CoVe checks claims against Tiekink et al. (2013). runPythonAnalysis performs DFT energy plots from paper data using NumPy, with GRADE scoring evidence strength for slipped carbocation stability.
Synthesize & Write
Synthesis Agent detects gaps in ligand design between Wang (2012) and recent works via contradiction flagging. Writing Agent uses latexEditText and latexSyncCitations to draft mechanisms, latexCompile for publication-ready schemes, and exportMermaid for carbocation intermediate diagrams.
Use Cases
"Plot energy profiles of gold-alkyne slipped carbocations from DFT data in gold catalysis papers."
Research Agent → searchPapers('gold alkyne DFT') → Analysis Agent → readPaperContent(Kumar 2014) → runPythonAnalysis(NumPy/matplotlib for energy diagrams) → researcher gets publication-quality plots with GRADE-verified data.
"Draft a review section on gold π-acid mechanisms with citations and schemes."
Synthesis Agent → gap detection(Tiekink 2013, Wang 2012) → Writing Agent → latexEditText('mechanism text') → latexSyncCitations → latexCompile → researcher gets compiled LaTeX PDF with synced references.
"Find GitHub repos with gold catalyst simulation code from alkyne activation papers."
Research Agent → citationGraph(Tiekink 2013) → Code Discovery workflow (paperExtractUrls → paperFindGithubRepo → githubRepoInspect) → researcher gets verified DFT codes linked to mechanistic studies.
Automated Workflows
Deep Research workflow systematically reviews 50+ gold catalysis papers via searchPapers → citationGraph → structured report on π-acid evolution from Tiekink (2013). DeepScan applies 7-step analysis with CoVe checkpoints to verify Kumar (2014) mechanisms against spectroscopy data. Theorizer generates hypotheses on ligand effects by synthesizing Wang (2012) with recent DFT insights.
Frequently Asked Questions
What defines gold π-acid catalysis of alkynes?
Gold(I) acts as a π-acid coordinating alkyne triple bonds to form slipped carbocations for nucleophilic attack, as detailed in Tiekink et al. (2013) and Kumar (2014).
What are common methods in this subtopic?
Methods include phosphine-ligated Au(I) for hydrofunctionalizations and DFT modeling of intermediates, per Wang (2012) and Kumar (2014).
What are key papers?
Foundational: Tiekink et al. (2013, 42 citations) on gold-π interactions; Kumar (2014) on mechanisms; Wang (2012) on nucleophilic additions.
What open problems exist?
Challenges include catalyst deactivation, ligand optimization for selectivity, and direct observation of slipped intermediates beyond DFT (Kumar 2014).
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Part of the Catalytic Alkyne Reactions Research Guide