Optimizing P,N‐Bidentate Ligands for Oxidative Gold Catalysis: Efficient Intermolecular Trapping of α‐Oxo Gold Carbenes by Carboxylic Acids
TLDR
A generally highly efficient and broadly applicable synthesis of carboxymethyl ketones from readily available carboxylic acids and terminal alkynes is developed under exceptionally mild reaction conditions.Abstract:
Steric Bulk or Conformation Control? Optimization of P,N-bidentate ligands reveals the importance of conformation control in the development of highly efficient intermolecular trapping of reactive α-oxo gold carbene intermediates. While a pendant piperidine ring offers suitable steric bulk, fixing its conformation to provide better shielding to the highly electrophilic carbene center turned out to be crucial for the excellent reaction efficiency. A generally highly efficient and broadly applicable synthesis of carboxymethyl ketones from readily available carboxylic acids and terminal alkynes is developed under exceptionally mild reaction conditions.read more
Citations
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Gold(I)-Catalyzed Activation of Alkynes for the Construction of Molecular Complexity
Ruth Dorel,Antonio M. Echavarren +1 more
TL;DR: Gold(I) complexes selectively activate π-bonds of alkenes in complex molecular settings, which has been attributed to relativistic effects as discussed by the authors, and are the most effective catalysts for the electrophilic activation of alkynes under homogeneous conditions.
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A Non-Diazo Approach to α-Oxo Gold Carbenes via Gold-Catalyzed Alkyne Oxidation
TL;DR: This Account shows that the unique access to the gold carbene species in homogeneous gold catalysis offers an opportunity to generate α-oxo gold carbenes if both nucleophile and electrophile are oxygen, which would enable readily available and safer alkynes to replace hazardous α-diazo carbonyl compounds as precursors in the realm of goldcarbene chemistry.
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Dioxygen-triggered oxidative radical reaction: direct aerobic difunctionalization of terminal alkynes toward β-keto sulfones.
TL;DR: Operando IR experiments revealed that pyridine not only acts as a base to successfully surpress ATRA (atom transfer radical addition) process, but also plays a vital role in reducing the activity of sulfinic acids.
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Intriguing mechanistic labyrinths in gold(I) catalysis
TL;DR: Gold(i) controls complex transformations proceeding through carbocationic species by stabilising the key reactive intermediates.
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New Approaches to the Synthesis of Metal Carbenes
TL;DR: Some of the most important breakthroughs in the generation, catalytic reactions, and selectivity control of metal carbenes from non-diazo starting compounds are summarized.
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Gold-Catalyzed Organic Reactions
TL;DR: Important vinylgold intermediates, the transmetalation from gold to other transition metals, the development of new ligands for gold catalysis, and significant contributions from computational chemistry are other crucial points for the field highlighted here.
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Catalytic Carbophilic Activation: Catalysis by Platinum and Gold π Acids
Alois Fürstner,Paul W. Davies +1 more
TL;DR: The ability of platinum and gold catalysts to effect powerful atom-economic transformations has led to a marked increase in their utilization and the application of platinum- and gold-catalyzed transformations in natural product synthesis is discussed.
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TL;DR: The ways in which selectivity can be controlled in homogeneous Au catalysis are enumerated, in the hope that lessons to guide catalyst selection and the design of new catalysts may be distilled from a thorough evaluation of ligand, counterion, and oxidation state effects as they influence chemo-, regio-, and stereoselectivity in homogeneity AuCatalysis.
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TL;DR: The proposed involvement of cyclopropyl metal carbenes of type 4 in the electrophilic activation of enynes by transition metals was first substantiated in reactions catalyzed by Pd(II), in which the initially formed cycloprostyl palladiumCarbenes undergo [4 + 2] cycloaddition with the double bond of the conjugate enyne.
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Zigang Li,Chad Brouwer,Chuan He +2 more
TL;DR: Thanks to gold-based catalysts, various organic transformations have been accessible under facile conditions with both high yields and chemoselectivity.