60492-39-9

Upstream product

• 100-42-5 styrene 
• 100-66-3 methoxybenzene 
• 98-85-1 1-Phenylethanol 
• 98-86-2 acetophenone 
• 4013-34-7 3-phenyl-2-oxabutane 
• 672-65-1 (1-chloroethyl)benzene 
• 336628-52-5 (5R,1'S)-5-chloromethyl-3-(1'-phenylethyl)-2-oxazolidinone 
• 17376-04-4 2-phenethyl iodide 
• 883-90-9 o-benzyl anisole 
• 74-88-4 methyl iodide 
• 93-92-5 1-phenylethyl acetate 
• 28994-41-4 o-Benzylphenol 
• 16197-93-6 (S)-1-phenylethyl acetate 
• 14856-75-8 1-phenyl-1-trimethylsilyloxyethane 

Downstream Products

• 4237-44-9 2-(1-phenylethyl)phenol 

Relevant academic research and scientific papers

Cascade Reductive Friedel-Crafts Alkylation Catalyzed by Robust Iridium(III) Hydride Complexes Containing a Protic Triazolylidene Ligand

The synthesis of complex molecules like active pharmaceutical ingredients typically requires multiple single-step reactions, in series or in a modular fashion, with laborious purification and potentially unstable intermediates. Cascade processes offer attractive synthetic remediation as they reduce time, energy, and waste associated with multistep syntheses. For example, triarylmethanes are traditionally prepared via several synthetic steps, and only a handful of cascade routes are known with limitations due to high catalyst loadings. Here, we present an expedient catalytic cascade process to produce triarylmethanes. For this purpose, we have developed a bifunctional iridium system as the efficient catalyst to build heterotriaryl synthons via reductive Friedel-Crafts alkylation from ketones, arenes, and hydrogen. The catalytically active species were generated in situ from a robust triazolyl iridium(III) hydride complex and acid and is composed of a metal-bound hydride and a proximal ligand-bound proton for reversible dihydrogen release. These complexes catalyze the direct hydrogenation of ketones at slow rates followed by dehydration. Appropriate adjustment of the conditions successfully intercepts this dehydration and leads instead to efficient C-C coupling and Friedel-Crafts alkylation. The scope of this cascade process includes a variety of carbonyl substrates such as aldehydes, (alkyl)(aryl)ketones, and diaryl ketones as precursor electrophiles with arenes and heteroarenes for Friedel-Crafts coupling. The reported method has been validated in a swift one-step synthesis of the core structure of a potent antibacterial agent. Excellent yields and exquisite selectivities were achieved for this cascade process with unprecedentedly low iridium loadings (0.02 mol %). Moreover, the catalytic activity of the protic system is significantly higher than that of an N-methylated analogue, confirming the benefit of the Ir-H/N-H hydride-proton system for high catalytic performance.

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.

[C^N]-Alkenyl Gold(III) Complexes by Proximal Ring-Opening of (2-Pyridyl)alkylidenecyclopropanes: Mechanistic Insights

Pyridine-substituted alkylidenecyclopropanes (Py-ACPs) react with gold(III) salts under mild reaction conditions through an unprecedented, proximal ring-opening pathway, to generate highly appealing, catalytically active pyridine alkenyl [C^N]-gold(III) species. Mechanistic studies reveal that the activation of the C?C bond of the ACP takes place through an unusual concerted, σ-bond metathesis type-process.

Nickel-Catalyzed Chain-Walking Cross-Electrophile Coupling of Alkyl and Aryl Halides and Olefin Hydroarylation Enabled by Electrochemical Reduction

The first electrochemical approach for nickel-catalyzed cross-electrophile coupling was developed. This method provides a novel route to 1,1-diarylalkane derivatives from simple and readily available alkyl and aryl halides in good yields and excellent regioselectivity under mild conditions. The procedure shows good tolerance for a broad variety of functional groups and both primary and secondary alkyl halides can be used. Furthermore, the reaction was successfully scaled up to the multigram scale, thus indicating potential for industrial application. Mechanistic investigation suggested the formation of a nickel hydride in the electroreductive chain-walking arylation, which led to the development of a new nickel-catalyzed hydroarylation of styrenes to provide a series of 1,1-diaryl alkanes in good yields under mild reaction conditions.

Regiodivergent DH or HD Addition to Alkenes: Deuterohydrogenation versus Hydrodeuterogenation

The regioselective and regiodivergent addition of H-D to a variety of 1,1-diarylalkenes was realized utilizing selectively deuterated dihydroaromatic compounds, which were generated by cobalt catalysis. The reaction was initiated by catalytic amounts of B

Synthesis and catalytic reactivity of mononuclear substituted tetramethylcyclopentadienyl molybdenum carbonyl complexes

The reactions of five dinuclear carbonyl complexes [(η 5-C5Me4R)Mo(CO)3]2 [R = allyl, n Bu, t Bu, Ph, Bz] with I2 in chloroform solution gave the corresponding mononuclear substituted tetramethylcyclopentadienyl molybdenum carbonyl complexes [(η 5-C5Me4R)MoI(CO)3] [R = allyl (1), n Bu (2), t Bu (3), Ph (4), Bz (5)]. The molecular structures of complexes 2, 3 and 5 were determined by X-ray diffraction analysis. The results show that the substituent in the ring can directly affect the Mo-I bond distances; the more sterically hindered the substituent, the longer the Mo-I bond. Friedel-Crafts reactions of aromatic compounds with a variety of alkylation reagents catalyzed by the complexes showed that all of these mononuclear molybdenum carbonyl complexes have catalytic activity in Friedel-Crafts alkylation reactions. Indeed, compared with traditional catalysts, these mononuclear metal carbonyl complexes have obvious advantages such as higher activities, mild reaction conditions, high selectivity, simple post-processing, and environmentally friendly chemistry.

Efficient hydroarylation and hydroalkenylation of vinylarenes by Br?nsted acid catalysis

Br?nsted acid Tf2NH alone catalyzed Friedel-Crafts-type hydroarylation and head-to-tail hydroalkenylation of vinylarenes under mild reaction conditions have been realized, providing a readily scalable, metal-free, and practical access to the 1,1-diarylalkane scaffolds and trans-1,3-diaryl-1-butenes in high yields and excellent regioselectivities.

Room Temperature Catalyst System for the Hydroarylation of Olefins

A simple protocol for the hydroarylation of olefins to yield diarylmethine products is described. A Friedel-Crafts-type synthetic strategy allows direct access to biorelevant products in high atom efficiency. A combination of substoichiometric amounts of TMSCl and ZnBr2 promotes a rapid hydroarylation process at ambient temperature. The method is high yielding and is amenable to scale-up protocols.

Transition-Metal-Free Stereospecific Cross-Coupling with Alkenylboronic Acids as Nucleophiles

We herein report a transition-metal-free cross-coupling between secondary alkyl halides/mesylates and aryl/alkenylboronic acid, providing expedited access to a series of nonchiral/chiral coupling products in moderate to good yields. Stereospecific SN2-type coupling is developed for the first time with alkenylboronic acids as pure nucleophiles, offering an attractive alternative to the stereospecific transition-metal-catalyzed C(sp2)-C(sp3) cross-coupling.

Iron-catalyzed friedel-crafts benzylation with benzyl TMS ethers at room temperature

Friedel-Crafts benzylations between unactivated arenes and benzyl alcohol derivatives are clean and straightforward processes to construct biologically useful di- and triarylmethanes. We have established an efficient iron-catalyzed Friedel-Crafts benzylation method at room temperature that uses benzyl TMS ethers as substrates, which are poorly reactive under common nucleophilic substitution conditions. The reaction seems to progress through iron-catalyzed self-condensation of the benzyl TMS ether to the corresponding dibenzylic ether. The use of excess arene relative to benzyl TMS ether produced mono-benzylated arene (diand tri-arylmethane products), whereas the use of excess benzyl TMS ether versus arene provided bis-benzylated arene (polyarylated products) in high yields and regioselectivities. In previous methods, the latter double Friedel-Crafts benzylations hardly proceed.