3717-68-8

Usage

Physical State

Colorless liquid

Odor

Sweet, floral

Common Uses

Fragrances, perfumes, dyes, pharmaceuticals

Stability

Relatively stable and non-reactive

Safety Precaution

Flammable, handle and store with care

Industrial and Commercial Applications

Production of fine chemicals, consumer products

Upstream product

• 585-71-7 (1-bromoethyl)benzne 
• 108-88-3 toluene 
• 100-42-5 styrene 
• 98-85-1 1-Phenylethanol 
• 672-65-1 (1-chloroethyl)benzene 
• 100-41-4 ethylbenzene 
• 106-49-0 p-toluidine 
• 7214-61-1 (1-nitroethyl)benzene 
• 52252-67-2 3,9-dimethyl-thioxanthene 
• 201230-82-2 carbon monoxide 
• 948-55-0 1-phenyl-1-p-tolyl-ethylene 
• 98-86-2 acetophenone 
• 10199-63-0 1-(3,5-dimethyl-1H-pyrazol-1-yl)ethanone 
• 93-92-5 1-phenylethyl acetate 

Downstream Products

• 611-95-0 4-carboxybenzophenone 
• 95126-98-0 1-phenyl-1-p-tolyl-ethyl hydroperoxide 
• 106-44-5 p-cresol 
• 98-86-2 acetophenone 
• 134-84-9 4-Methylbenzophenone 

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.

Reductive activation and hydrofunctionalization of olefins by multiphoton tandem photoredox catalysis

The conversion of olefin feedstocks to architecturally complex alkanes represents an important strategy in the expedient generation of valuable molecules for the chemical and life sciences. Synthetic approaches are reliant on the electrophilic activation of unactivated olefins, necessitating functionalization with nucleophiles. However, the reductive functionalization of unactivated and less activated olefins with electrophiles remains an ongoing challenge in synthetic chemistry. Here, we report the nucleophilic activation of inert styrenes through a photoinduced direct single electron reduction to the corresponding nucleophilic radical anion. Central to this approach is the multiphoton tandem photoredox cycle of the iridium photocatalyst [Ir(ppy)2(dtbbpy)] PF6, which triggers in situ formation of a high-energy photoreductant that selectively reduces styrene olefinic π bonds to radical anions without stoichiometric reductants or dissolving metals. This mild strategy enables the chemoselective reduction and hydrofunctionalization of styrenes to furnish valuable alkane and tertiary alcohol derivatives. Mechanistic studies support the formation of a styrene olefinic radical anion intermediate and a Birch-type reduction involving two sequential single electron transfers. Overall, this complementary mode of olefin activation achieves the hydrofunctionalization of less activated alkenes with electrophiles, adding value to abundant olefins as valuable building blocks in modern synthetic protocols.

Iron-catalysed enantioconvergent Suzuki-Miyaura cross-coupling to afford enantioenriched 1,1-diarylalkanes

The first stereoconvergent Suzuki-Miyaura cross-coupling reaction was developed to afford enantioenriched 1,1-diarylalkanes. An iron-based complex containing a chiral cyanobis(oxazoline) ligand framework was best to obtain enantioenriched 1,1-diarylalkanes from cross-coupling reactions between unactivated aryl boronic esters and benzylic chlorides. Enhanced yields were obtained when 1,3,5-trimethoxybenzene was used as an additive, which is hypothesized to extend the lifetime of the iron-based catalyst. Exceptional enantioselectivities were obtained with challenging ortho-substituted benzylic chlorides. This journal is

Nickel-Catalyzed Electrochemical Reductive Relay Cross-Coupling of Alkyl Halides to Aryl Halides

A highly regioselective Ni-catalyzed electrochemical reductive relay cross-coupling between an aryl halide and an alkyl halide has been developed in an undivided cell. Various functional groups are tolerated under these mild reaction conditions, which pro

Bisoxazoline-pincer ligated cobalt-catalyzed hydrogenation of alkenes

The efficient and atom economical hydrogenation of alkenes using a novel bisoxazoline ligated cobalt complex has been developed. The hydrogenation of a variety of alkenes containing electron neutral and electron-donating groups proceeds in high yield, whi

Nickel(0)-Catalyzed Hydroarylation of Styrenes and 1,3-Dienes with Organoboron Compounds

A Ni-catalyzed hydroarylation of styrenes and 1,3-dienes with organoboron compounds has been developed. The reaction offers a highly selective approach to diarylalkanes and allylarenes under redox-neutral conditions. In this hydroarylation reaction, a new strategy that uses the proton of methanol to generate the active catalyst species Ni?H was developed. The Ni-catalyzed hydroarylation, combined with a Ir-catalyzed C?H borylation, affords a very efficient and straightforward access to a retinoic acid receptor agonist.

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.

Feedstocks to Pharmacophores: Cu-Catalyzed Oxidative Arylation of Inexpensive Alkylarenes Enabling Direct Access to Diarylalkanes

A Cu-catalyzed method has been identified for selective oxidative arylation of benzylic C-H bonds with arylboronic esters. The resulting 1,1-diarylalkanes are accessed directly from inexpensive alkylarenes containing primary and secondary benzylic C-H bonds, such as toluene or ethylbenzene. All catalyst components are commercially available at low cost, and the arylboronic esters are either commercially available or easily accessible from the commercially available boronic acids. The potential utility of these methods in medicinal chemistry applications is highlighted.

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.