2713-41-9

Upstream product

• 145919-50-2 6,6-difluorobicyclo<3.1.0>hex-2-ene 
• 758-12-3 deuteroacetic acid 
• 88284-48-4 2-(trimethylsilyl)phenyl trifluoromethanesulfonate 
• 462-06-6 fluorobenzene 
• 811-98-3 d⁽⁴⁾-methanol 
• 1391933-28-0 hydrido[bis(pentafluorophenyl)][2-(2,2,6,6-tetramethylpiperidinium-1-yl)phenyl]borate^(1-) 
• 367-11-3 ortho-difluorobenzene 

Relevant academic research and scientific papers

Diphenyliodonium-Catalyzed Fluorination of Arynes: Synthesis of ortho-Fluoroiodoarenes

Described is a one-pot vicinal fluorination-iodination of arynes at room temperature. The diphenyliodonium salt proved to be a privileged catalyst for this nucleophilic fluorination process using CsF as a fluorine source, and a subsequent facile electrophilic iodination with C4F9I was also found to be crucial to ensure the efficient fluorination. This new synthetic protocol has a broad substrate scope under mild reaction conditions.

Catalytic Hydrogenolysis of Aryl C-F Bonds Using a Bimetallic Rhodium-Indium Complex

A homogeneous rhodium-indium catalyst hydrodefluorinates substrates bearing strong aryl C-F bonds, including difluoro- and fluorobenzene, using 1 atm of H2, alkoxide bases, and moderate temperatures (70-90 °C). Characterization of catalytic intermediates establishes a formal Rh-I/RhI redox cycle. The Rh → In interaction is proposed to enable catalysis by stabilizing the reactive Rh-I species, which is responsible for cleaving the Ar-F bond and is ultimately regenerated using H2 and base.

Deuterium Exchange between Arenes and Deuterated Solvents in the Absence of a Transition Metal: Synthesis of D-Labeled Fluoroarenes

Fluoroarenes can be selectively deuterated by H/D exchange with common deuterated solvents in the presence of a catalytic amount of an alkali metal carbonate or, for the less acidic arenes, stoichiometric quantities of potassium phosphate. This is a susta

Mechanistic Insight into H/D Exchange by a Pentanuclear Ni-H Cluster and Synthesis and Characterization of Structural Analogues of Potential Intermediates

Experiments to gain mechanistic insight into catalytic H/D exchange of unactivated arenes by [(iPr3P)Ni]5H6 (1) are described. The reaction order with respect to 1, arene substrate, and added iPr3P were determined, as well as the temperature dependence of reaction rate. Site-selectivity data were obtained by monitoring the reaction of 1 with fluorobenzene and 2-methoxynaphthalene. H/D exchange competition reactions between arenes reacted with 1 were performed. The addition of an excess of Hg to a solution of 1 provided the new heterometallic cluster [(iPr3P)Ni]5H6(μ4-Hg) (2); this species also undergoes H/D exchange with C6D6, albeit more slowly than 1. Reaction of cluster 1 with TlCp (Cp = C5H5) gave (η5-Cp)Ni[(iPr3P)Ni]4(μ2-H)4(μ4-Tl) (3) with the loss of H2. A similar transfer of cyclopentadienyl to Ni occurred when 1 was reacted with MgCp2, to give (η5-Cp)Ni[(iPr3P)Ni]4H6(μ4-MgCp) (4), but not H2 loss. Reaction of 1 with cyclopentadiene gave the 5-coordinate hydride complex (η5-Cp)Ni[(iPr3P)Ni]4(μ2-H)4(μ5-H) (5). The Cp? analogue, (η5-Cp)Ni[(iPr3P)Ni]4(μ2-H)4(μ5-H) (6) (where Cp? = C5Me5), was synthesized by reacting 1 with LiCp? in THF, or by reaction of 1 with pentamethylcyclopentadiene.

Sodium Diisopropylamide in Tetrahydrofuran: Selectivities, Rates, and Mechanisms of Arene Metalations

Sodium diisopropylamide (NaDA)-mediated metalations of arenes in tetrahydrofuran (THF)/hexane or THF/Me2NEt solutions are described. A survey of >40 benzenoid- and pyridine-based arenes with a range of substituents demonstrates the efficacy and regioselectivity of metalation. Metalations of activated disubstituted arenes and selected monosubstituted arenes are rapid at -78 °C. Rate studies of 1,3-dimethoxybenzene and related methoxylated arenes show exclusively monomer-based orthometalations with two or three coordinated THF ligands. Rate studies of the isotopic exchange of benzene and monosubstituted arenes with weakly activating groups reveal analogous di- and trisolvated monomer-based metalations. Cooperative inductive, mesomeric, steric, and chelate effects are discussed.

Metal-Free sp2-C-H Borylation as a Common Reactivity Pattern of Frustrated 2-Aminophenylboranes

C-H borylation is a powerful and atom-efficient method for converting affordable and abundant chemicals into versatile organic reagents used in the production of fine chemicals and functional materials. Herein we report a facile C-H borylation of aromatic and olefinic C-H bonds with 2-aminophenylboranes. Computational and experimental studies reveal that the metal-free C-H insertion proceeds via a frustrated Lewis pair mechanism involving heterolytic splitting of the C-H bond by cooperative action of the amine and boryl groups. The adapted geometry of the reactive B and N centers results in an unprecedentently low kinetic barrier for both insertion into the sp2-C-H bond and intramolecular protonation of the sp2-C-B bond in 2-ammoniophenyl(aryl)- or -(alkenyl)borates. This common reactivity pattern serves as a platform for various catalytic reactions such as C-H borylation and hydrogenation of alkynes. In particular, we demonstrate that simple 2-aminopyridinium salts efficiently catalyze the C-H borylation of hetarenes with catecholborane. This reaction is presumably mediated by a borenium species isoelectronic to 2-aminophenylboranes.

The thermal conversions of 6,6-difluorobicyclo[3.1.0]hex-2-enes to fluorobenzenes. An interesting dichotomy of mechanisms

A kinetic study of the thermal, dehydrofluorinative aromatization reactions of two ostensibly-similar 6,6-difluorobicyclo[3.1.0]hex-2-ene systems led to the conclusion that drastically different mechanisms operate for the two reactions. Activation parameters, solvent effects, kinetic isotope effects, isotope labelling experiments and observation of reactive intermediates all contributed to the conclusion that the reaction of 6,6-difluorobicyclo[3.1.0]hex-2-ene, 1, proceeds via a homolytic hydrogen-shift rearrangement, while the reaction of 2,3-benzo-6,6-difluorobicyclo[3.1.0]hex-2-ene, 6, proceeds via a solvolytic mechanism involving rate-determining carbocation formation.