A5046524679- Catalytic C–H Functionalization Methods
- Crystallization and Solubility Studies
- X-ray Diffraction in Crystallography
- Synthetic Organic Chemistry Methods
- Asymmetric Synthesis and Catalysis
- Catalytic Alkyne Reactions
- Asymmetric Hydrogenation and Catalysis
- Synthesis and Catalytic Reactions
- Cyclopropane Reaction Mechanisms
- Chemical synthesis and alkaloids
- Oxidative Organic Chemistry Reactions
- Sulfur-Based Synthesis Techniques
- Fluorine in Organic Chemistry
- Crystallography and molecular interactions
- Catalytic Cross-Coupling Reactions
- Chemical Synthesis and Analysis
- Organoboron and organosilicon chemistry
- Chemical Synthesis and Reactions
- Traditional and Medicinal Uses of Annonaceae
- Synthesis of Indole Derivatives
- Vanadium and Halogenation Chemistry
- Particle Detector Development and Performance
- Particle physics theoretical and experimental studies
- Organometallic Complex Synthesis and Catalysis
- Cyclization and Aryne Chemistry
Institut de Science et d'Ingénierie Supramoléculaires
2020-2024
Université de Strasbourg
2020-2024
Centre National de la Recherche Scientifique
2015-2024
CEA Paris-Saclay
2005-2024
Commissariat à l'Énergie Atomique et aux Énergies Alternatives
2005-2024
Institut de Recherche sur les Lois Fondamentales de l'Univers
2014-2024
Université de Haute-Alsace
2024
Université Paris-Saclay
2016-2021
Institut de Chimie Moléculaire et des Matériaux d'Orsay
2014-2021
Université Paris-Sud
2012-2021
Hexafluoroisopropanol (HFIP) is a solvent with unique properties that has recently gained attention for promoting wide range of challenging chemical reactions. It was initially believed HFIP almost exclusively involved in the stabilization cationic intermediates, owing to its high polarity and low nucleophilicity. However, many cases, mechanism action appears be more complex. Recent findings reveal Lewis Brønsted acid-catalyzed transformations conducted additionally involve cooperation...
Photocatalysis has become a prominent tool in the arsenal of organic chemists to develop and (re)imagine transformations. However, only handful versatile photocatalysts (PCs) are available, hampering discovery new reactivities. Here, we report design complete physicochemical characterization 9-aryl dihydroacridines (9ADA) 12-aryl dihydrobenzoacridines (12ADBA) as strong reducing PCs. Punctual structural variations modulate their molecular orbital distributions unlock locally or...
Aniline derivatives are frequently encountered in molecules of industrial relevance such as dyes or antioxidants, which make the development synthetic methods for functionalization these privileged structures highly sought-after. A general protocol hydroarylation electronically diverse alkenes with anilines would be ideal to provide densely functionalized compounds. However, this transformation has been underexplored compared more traditional unactivated because significant challenges...
Alcohols and epoxides are arguably ideal electrophiles for the Friedel-Crafts alkylation, since they widely available, require no pre-activation, produce stoichiometric waste beyond water. However, neither primary aliphatic alcohols nor most classes of terminal compatible with existing intermolecular methodologies, sequential reactions starting from consequently remain underexplored. Here, we report that these limitations easily overcome using Brønsted acid catalysis in hexafluoroisopropanol...
In the past 5 years, hexafluoroisopropanol (HFIP) has been used as a unique solvent or additive to enable challenging transformations through substrate activation and stabilization of reactive intermediates. this Review, we aim at describing difunctionalization processes which were unlocked when HFIP was involved. Specifically, focus on cyclizations additions alkenes, alkynes, epoxides, carbonyls that introduce wide range functional groups interest.
Working three shifts: Polyconjugated δ-diketones are formed stereoselectively in high yields by the gold-catalyzed rearrangement of 1,6-diyn-3-yl esters. This cascade involves a 1,3-sigmatropic acyloxy shift, 5-exo-dig cyclization resulting allenyne, and an unprecedented 1,5-sigmatropic shift acyl fragment. The usefulness products was shown efficient acid-catalyzed transformation into complex polycyclic framework. Detailed facts importance to specialist readers published as "Supporting...
Abstract From a series of gold complexes the type [ t‐ BuXPhosAu(MeCN)]X (X=anion), best results in intermolecular gold(I)‐catalyzed reactions are obtained with complex bulky and soft anion BAr 4 F− [BAr =3,5‐bis(trifluoromethyl)phenylborate] improving original protocols by 10–30% yield. A kinetic study on [2+2] cycloaddition reaction alkynes alkenes is consistent an scenario which rate‐determining step ligand exchange to generate (η 2 ‐phenylacetylene)gold(I) complex. We have studied detail...
A general reaction sequence is described that involves Nazarov cyclization followed by two sequential Wagner-Meerwein migrations, to afford spirocyclic compounds from divinyl ketones in the presence of 1 equiv copper(II) complexes. detailed investigation this including a study substrate scope and limitations. It was found after 4π electrocyclization, different pathways are available oxyallyl cation intermediate: elimination proton can give usual cycloadduct, or ring contraction an...
A combination of a calcium(II) triflimide salt and hexafluoroisopropanol (HFIP) was found to be highly efficient promoter system for the intra- intermolecular hydroamidation unactivated alkenes. Unlike other methods, vast array functional groups is tolerated at nitrogen alkene moieties. The reaction produces corresponding nitrogen-containing compounds in excellent yields good diastereoselectivities. use HFIP as solvent proved crucial proper carrying out this transformation. Its role, well...
Highly functionalized cyclopentenones can be generated by a chemoselective copper(II)-mediated Nazarov/Wagner–Meerwein rearrangement sequence of divinyl ketones. A detailed investigation this is described including study substrate scope and limitations. After the initial 4π electrocyclization, reaction proceeds via two different sequential [1,2]-shifts, with selectivity that depends upon either migratory ability or steric bulkiness substituents at C1 C5. This methodology allows creation...
A challenging catalytic hydroarylation of highly electron deficient styrenes has been developed on the basis efficient cooperation between a calcium(II) triflimide salt and hexafluoroisopropanol (HFIP). This method affords large variety diaryl alkanes, notably ethanes, in good to excellent yields, is simple implement compatible with various functional groups. Furthermore, DFT calculations deuterium labeling experiments were conducted elucidate function this promoter system.
The first examples of calcium-catalyzed aza-Piancatelli reactions between substituted 2-furylcarbinols and aniline derivatives are described. A variety 4-aminocyclopentenones have been synthesized stereoselectively in high yields. experimental procedure utilizes simple salts does not require specific precautions.
Abstract A method to extend the scope of aza‐Piancatelli reaction between 2‐furylcarbinols and anilines is depicted. We found that 1,1,1,3,3,3‐hexafluoro‐2‐propanol (HFIP) solvent choice for this transformation, as it outcompetes usual solvents in terms rate yield. Side reactions other issues raised by title are prevented, thereby providing an avenue complex molecules were previously inaccessible. Lewis acidity studies computations carried out unveil role HFIP. Based on these results, we...
The reduction of epoxides is a powerful tool to access anti-Markovnikov alcohols, but reported methods are poorly compatible with strongly electronically deactivated substrates. Here, we describe general method for the linear-selective styryl oxides incorporating strong electron-withdrawing groups. remains more traditional epoxide motifs, such as aliphatic and electron-rich styrene oxides. Other (hetero)cycles oxetanes, tetrahydrofurans, aziridines, cyclopropanes can also be reductively...
Sulfoximines make up a class of compounds growing interest for crop science and medicinal chemistry, but methods directly incorporating them into complex molecular scaffolds are lacking. Here we report scandium-catalyzed variant the aza-Piancatelli cyclization that can incorporate sulfoximines as nucleophiles rather than classical aniline substrates. Starting from 2-furylcarbinols sulfoximines, reaction provides direct access to 4-sulfoximinocyclopentenones, new scaffold bearing...
Three-ring circus: An expedient route to tricyclic fused 2-trimethylsilyl-3-aminopyridines exhibiting unprecedented skeletons is described. The key step a very efficient cobalt-catalyzed [2+2+2] cycloaddition of polyunsaturated compound displaying an ynamide, alkyne, and nitrile functionality (see picture). first cocyclizations between ynamides, nitriles, alkynes are reported. They open new access nitrogen-containing heterocycles type 2-trimethylsilyl-3-aminopyridines. Such frameworks, which...
The gold(I)-catalyzed [2 + 2] cycloaddition of large 1,n-enynes (n = 10–16) provides access to 9- 15-membered ring macrocycles incorporating a cyclobutene moiety. reaction requires the use gold(I) catalyst bearing sterically hindered biphenylphosphine ligand.
A heart of gold: Phenols can be obtained by the intermolecular reaction furans with alkynes using [AuIPr](+)A(-) catalysts (see scheme). 1,3-Diphenylisobenzofuran also reacts via a cyclopropyl gold carbene to selectively form 2,3-disubstituted indenes. (IPr = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene; anion.).
ADVERTISEMENT RETURN TO ISSUEPREVCommunicationNEXTHighly Enantioselective Rhodium-Catalyzed [2+2+2] Cycloaddition of Diynes to SulfoniminesMuriel Amatore, David Lebœuf, Max Malacria, Vincent Gandon*, and Corinne Aubert*View Author Information UPMC UNIV Paris 06, Institut Parisien de Chimie Moléculaire, UMR CNRS 7201, Case 229, 4 Place Jussieu, 75252 Cedex 05, France[email protected]; [email protected]Cite this: J. Am. Chem. Soc. 2013, 135, 12, 4576–4579Publication Date (Web):March 4,...
Highly functionalized cyclopentenones are prepared stereospecifically based on a chemoselective copper(II)-mediated Nazarov/Wagner-Meerwein rearrangement sequence. After the initial 4π electrocyclization, this reaction involves two sequential [1,2]-migrations depending upon both migratory ability and steric bulk of substituents at C1 C5. This sequence can be achieved by using catalytic quantity copper(II) in combination with weak Lewis acid. The mechanism is also supported DFT computations.
A new and efficient reaction sequence between 2-furylcarbinols, anilines, α-haloamides has been developed to afford highly functionalized cyclopenta[b]piperazinones. This transformation was accomplished through an aza-Piancatelli cyclization/azaoxyallyl cation trapping with a complete control of the diastereoselectivity.
Herein, we report the preparation of bridged tetrahydrobenzo[b]azepines, which was accomplished through an aza-Piancatelli cyclization/Michael addition sequence in a one-pot fashion from readily available precursors. It is noteworthy that general method to access these scaffolds hitherto unprecedented. Additionally, multifaceted aspects this process have been exemplified its application synthesis 2-azabicyclo[3.2.1]octanes and tetrahydrobenzo[b]oxepines, along with post-derivatizations.
Pyrrolidine and piperidine derivatives bearing halide functional groups are prevalent building blocks in drug discovery as halides can serve an anchor for post-modifications. In principle, one of the simplest ways to build these frameworks is haloamination alkenes. While progress has been made this field, notably with development enantioselective versions, reaction still fraught limitations terms reactivity. Besides, a major question remaining understand mechanism at work. The formation...
β-Arylethylamines are prevalent structural motifs in molecules exhibiting biological activity. Here we report a sequential one-pot protocol for the 1,2-aminoarylation of alkenes with hydroxylammonium triflate salts and (hetero)arenes. Unlike existing methods, this reaction provides direct entry to unprotected β-arylethylamines remarkable functional group tolerance, allowing key drug-oriented groups be installed two-step process. The use hexafluoroisopropanol as solvent combination an...