56913-50-9

Upstream product

• 108-86-1 bromobenzene 
• 83088-73-7 Trifluoro-acetic acid 1-(4-bromo-phenyl)-ethyl ester 
• 122948-58-7 1-(4-bromophenyl)vinyl trifluoromethanesulfonate 
• 71-43-2 benzene 
• 1374996-88-9 (4-bromophenyl)(phenyl)methyl 2,2,2-trichloroacetimidate 
• 75-24-1 trimethylaluminum 
• 29334-16-5 phenyl(4-bromophenyl)methanol 
• 4333-76-0 1-(4-bromophenyl)-1-phenylethene 
• 90-90-4 (4-bromophenyl)(phenyl)methanone 
• 4426-21-5 oxybis(diphenylborane) 
• 75230-51-2 4-bromoacetophenone tosylhydrazone 

Downstream Products

• 90-90-4 (4-bromophenyl)(phenyl)methanone 

Relevant academic research and scientific papers

Indium Tribromide-Catalysed Transfer-Hydrogenation: Expanding the Scope of the Hydrogenation and of the Regiodivergent DH or HD Addition to Alkenes

The transfer-hydrogenation as well as the regioselective and regiodivergent addition of H?D from regiospecific deuterated dihydroaromatic compounds to a variety of 1,1-di- and trisubstituted alkenes was realised with InBr3 in dichloro(m)ethane. In comparison with the previously reported BF3?Et2O-catalysed process, electron-deficient aryl-substituents can be applied reliably and thereby several restrictions could be lifted, and new types of substrates could be transformed successfully in hydrodeuterogenation as well as deuterohydrogenation transfer-hydrogenation reactions.

Teaching an old carbocation new tricks: Intermolecular C-H insertion reactions of vinyl cations

Vinyl carbocations have been the subject of extensive experimental and theoretical studies over the past five decades. Despite this long history in chemistry, the utility of vinyl cations in chemical synthesis has been limited, with most reactivity studies focusing on solvolysis reactions or intramolecular processes. Here we report synthetic and mechanistic studies of vinyl cations generated through silylium-weakly coordinating anion catalysis. We find that these reactive intermediates undergo mild intermolecular carbon-carbon bond-forming reactions, including carbon-hydrogen (C-H) insertion into unactivated sp3 C-H bonds and reductive Friedel-Crafts reactions with arenes. Moreover, we conducted computational studies of these alkane C-H functionalization reactions and discovered that they proceed through nonclassical, ambimodal transition structures. This reaction manifold provides a framework for the catalytic functionalization of hydrocarbons using simple ketone derivatives.

Synthesis of 1,1′-diarylethanes and related systems by displacement of trichloroacetimidates with trimethylaluminum

Benzylic trichloroacetimidates are readily displaced by trimethylaluminum under Lewis acid promoted conditions to provide the corresponding methyl substitution product. This method is a convenient way to access 1,1′-diarylethanes and related systems, which play a significant role in medicinal chemistry, with a number of systems owing their biological activity to this functionality. Most benzylic substrates undergo ready displacement, with electron deficient systems being the exception. The use of an enantiopure imidate showed significant racemization, implicating the formation of a cationic intermediate.

Br?nsted Acid-Catalyzed Transfer Hydrogenation of Imines and Alkenes Using Cyclohexa-1,4-dienes as Dihydrogen Surrogates

Cyclohexa-1,4-dienes are introduced to Br?nsted acid-catalyzed transfer hydrogenation as an alternative to the widely used Hantzsch dihydropyridines. While these hydrocarbon-based dihydrogen surrogates do offer little advantage over established protocols in imine reduction as well as reductive amination, their use enables the previously unprecedented transfer hydrogenation of structurally and electronically unbiased 1,1-di- and trisubstituted alkenes. The mild procedure requires 5.0 mol % of Tf2NH, but the less acidic sulfonic acids TfOH and TsOH work equally well.

B(C6F5)3-Catalyzed Transfer of Dihydrogen from One Unsaturated Hydrocarbon to Another

A transition-metal-free transfer hydrogenation of 1,1-disubstituted alkenes with cyclohexa-1,4-dienes as the formal source of dihydrogen is reported. The process is initiated by B(C6F5)3-mediated hydride abstraction from the dihydrogen surrogate, forming a Bronsted acidic Wheland complex and [HB(C6F5)3]-. A sequence of proton and hydride transfers onto the alkene substrate then yields the alkane. Although several carbenium ion intermediates are involved, competing reaction channels, such as dihydrogen release and cationic dimerization of reactants, are largely suppressed by the use of a cyclohexa-1,4-diene with methyl groups at the C1 and C5 as well as at the C3 position, the site of hydride abstraction. The alkene concentration is another crucial factor. The various reaction pathways were computationally analyzed, leading to a mechanistic picture that is in full agreement with the experimental observations.

Electrophilic Fluorophosphonium Cations in Frustrated Lewis Pair Hydrogen Activation and Catalytic Hydrogenation of Olefins

The combination of phosphorus(V)-based Lewis acids with diaryl amines and diaryl silylamines promotes reversible activation of dihydrogen and can be further exploited in metal-free catalytic olefin hydrogenation. Combined experimental and density functional theory (DFT) studies suggest a frustrated Lewis pair type activation mechanism. FLP hydrogenation: The combination of a phosphorus(V)-based Lewis acid with diaryl amines or diaryl silylamines promotes reversible activation of dihydrogen and can be further exploited in metal-free catalytic olefin hydrogenation. Combined experimental and density functional theory (DFT) studies suggest a frustrated Lewis pair (FLP)-type activation mechanism.

Synthesis of diarylmethanes via metal-free reductive cross-coupling of diarylborinic acids with tosyl hydrazones

This paper describes a practical and efficient procedure that takes advantage of diarylborinic acids as a cost-effective alternative to arylboronic acids for synthesis of diarylmethanes through metal-free reductive cross-coupling with N-tosylhydrazones of aromatic aldehydes and ketones. The procedure tolerates hydroxyl, halide, amine, and allyl functionality, complementary to the transition-metal catalyzed cross-coupling techniques.

Zinc chloride enhanced arylations of secondary benzyl trifluoroacetates in the presence of b-hydrogen atoms

Zinc or swim: Arylation of benzyl trifluoroacetates with arylzinc reagents in the presence of β- hydrogen atoms were realized under mild conditions. Both electron-rich and electron-deficient arene substrates were successfully arylated. This arylation method could offer a very versatile synthetic route to access a series of diversity-oriented diarylalkane motifs. TFA = trifluoroacetyl. Copyright