104175-13-5

Upstream product

• 24165-63-7 1-p-tolyl-3-buten-1-ol 
• 3160-38-1 (E)-4-p-tolylbut-3-en-2-one 
• 4023-84-1 4-(p-tolyl)-3-buten-2-one 
• 544-97-8 dimethyl zinc(II) 
• 1504-75-2 3-(4-methylphenyl)acrylaldehyde 
• 1237540-32-7 ((4-fluorophenyl)ethynyl)magnesium bromide 
• 56578-35-9 4-methyl-cinnamaldehyde 
• 75-16-1 methylmagnesium bromide 
• 598-32-3 2-hydroxy-3-butene 
• 106-49-0 p-toluidine 
• 64-17-5 ethanol 
• 101671-00-5 (E)-2-(4-methylphenyl)-1-nitroethene 
• 459-44-9 4-methylbenzenediazonium tetrafluoroborate 
• 104-87-0 4-methyl-benzaldehyde 

Downstream Products

• 7774-79-0 4-(4-methylphenyl)butan-2-one 
• 3160-38-1 (E)-4-p-tolylbut-3-en-2-one 
• 855518-88-6 1-methyl-4-(3-vinyloxy-but-1-enyl)-benzene 
• 1373490-27-7 (E)-2-methyl-5-(4-(p-tolyl)but-3-en-2-yl)thiophene 
• 1587713-37-8 (Z)-4-(4-(p-tolyl)but-3-en-2-yl)morpholine 
• 1587713-19-6 (E)-4-(4-(p-tolyl)but-3-en-2-yl)morpholine 
• 32507-41-8 1-(buta-1,3-dien-1-yl)-4-methylbenzene 
• 1261958-97-7 1-(3-benzyloxybut-1-enyl)-4-methylbenzene 
• 1242077-04-8 (E)-4-phenyl-1-(4-p-tolylbut-3-en-2-yl)-1H-1,2,3-triazole 

Relevant academic research and scientific papers

Silylated organometals: A family of recyclable homogeneous catalysts

A general strategy has been developed to synthesize a family of silylated organometals (M-PPh2-TS and DPEN-Ru-PPh2-Ts, M = Pd2+, Rh+, Pt2+, Ir+, or Ru2+, PPh2-Ts = PPh2CH2CH2Si(OEt)3), DPEN = (1R,2R)-1,2-diphenylethylenediamine). They can act as homogeneous catalysts with high efficiencies in various organic reactions using THF, CH2Cl2 or toluene as the reaction medium. After reaction, they could be thoroughly settled down by adding pentane and then used repeatedly owing to the complete catalyst recovery and good preservation of the catalyst structure. This is particularly important due to the increasing concerns regarding the cost, toxicity and limited availability of these nonrenewable transition metals.

Synthesis and anticancer activity of novel halolactones with β-aryl substituents from simple aromatic aldehydes

A series of 20 novel racemic iodo-, bromo- and chlorolactones, possessing β-phenyl-γ-lactone or β-phenyl-δ-lactone framework, were synthesized from commercially available aromatic aldehydes in convenient five-step syntheses. Some of them showed noticeable cytotoxic effect against two cancer lines, Jurkat (human leukaemia) and D17 (canine osteosarcoma). The highest activity, comparable with carboplatin, was observed for cis-5-(1-iodoethyl)-4-(4′-isopropylphenyl)dihydrofuran-2-one against Jurkat cell line.

Copper(i) pyrimidine-2-thiolate cluster-based polymers as bifunctional visible-light-photocatalysts for chemoselective transfer hydrogenation of α,β-unsaturated carbonyls

The photoinduced chemoselective transfer hydrogenation of unsaturated carbonyls to allylic alcohols has been accomplished using cluster-based MOFs as bifunctional visible photocatalysts. Assemblies of hexanuclear clusters [Cu6(dmpymt)6] (1, Hdmpymt = 4,6-dimethylpyrimidine-2-thione) as metalloligands with CuI or (Ph3P)CuI yielded cluster-based metal organic frameworks (MOFs) {[Cu6(dmpymt)6]2[Cu2(μ-I)2]4(CuI)2}n (2), {[Cu6(dmpymt)6]2[Cu2(μ-I)2]4}n (3), respectively. Nanoparticles (NPs) of 2 and 3 served both as photosensitizers and photocatalysts for the highly chemoselective reduction of unsaturated carbonyl compounds to unsaturated alcohols with high catalytic activity under blue LED irradiation. The photocatalytic system could be reused for several cycles without any obvious loss of efficiency.

Stereodivergent Pd/Cu Catalysis for the Dynamic Kinetic Asymmetric Transformation of Racemic Unsymmetrical 1,3-Disubstituted Allyl Acetates

A stereodivergent Pd/Cu catalyst system has been developed for the unprecedented dynamic kinetic asymmetric transformation (DyKAT) of racemic unsymmetrical 1,3-disubstituted allylic acetates with prochiral aldimine esters. A series of α,α-disubstituted α-amino acids bearing vicinal stereocenters were easily prepared with excellent enantioselectivities (up to >99% ee) and diastereoselectivities (up to >20:1 dr). Moreover, all four stereoisomers of the product can be readily obtained simply by switching the configurations of the two chiral metal catalysts. Furthermore, the present work highlights the power of synergistic Pd/Cu catalysis consisting of two common bidentate chiral ligands for stereodivergent synthesis.

Biocatalytic Enantioselective Oxidation of Sec-Allylic Alcohols with Flavin-Dependent Oxidases

The oxidation of allylic alcohols is challenging to perform in a chemo- as well as stereo-selective fashion at the expense of molecular oxygen using conventional chemical protocols. Here, we report the identification of a library of flavin-dependent oxidases including variants of the berberine bridge enzyme (BBE) analogue from Arabidopsis thaliana (AtBBE15) and the 5-(hydroxymethyl)furfural oxidase (HMFO) and its variants (V465T, V465S, V465T/W466H and V367R/W466F) for the enantioselective oxidation of sec-allylic alcohols. While primary and benzylic alcohols as well as certain sugars are well known to be transformed by flavin-dependent oxidases, sec-allylic alcohols have not been studied yet except in a single report. The model substrates investigated were oxidized enantioselectively in a kinetic resolution with an E-value of up to >200. For instance HMFO V465S/T oxidized the (S)-enantiomer of (E)-oct-3-en-2-ol (1 a) and (E)-4-phenylbut-3-en-2-ol with E>200 giving the remaining (R)-alcohol with ee>99% at 50% conversion. The enantioselectivity could be decreased if required by medium engineering by the addition of cosolvents (e. g. dimethyl sulfoxide).

A catalytic allylic cation-induced intermolecular allylation-semipinacol rearrangement

A catalytic intermolecular semipinacol rearrangement induced by allylic carbocations has been realized. This tandem reaction is highly efficient under the catalysis of ZnBr2, generating a wide range of α-homoallyl substituted ketones which contain all-carbon quaternary centres in good to excellent yields (up to 98%) with moderate to high diastereoselectivities (up to >20?:?1). Synthetic application of this novel methodology in the construction of core structures of natural products is also reported.

Enzymatic cascades for the stereo-complementary epimerisation of in situ generated epoxy alcohols

The synthesis of optically pure secondary epoxy alcohols from racemic allylic alcohols using a single whole-cell biocatalyst of recombinant Escherichia coli coexpressing three oxidoreductases is described. The cascade involves the concurrent action of a styrene monooxygenase that catalyzes the formation of the chiral epoxy group, and two alcohol dehydrogenases that fulfil the epimerisation of the hydroxy group. Two sets of alcohol dehydrogenases were each applied to couple with styrene monooxygenase in order to realize the epimerisation in a stereo-complementary manner. Excellent enantio- and diastereo-selectivities were achieved for most of the 12 substrates.

Chemo-, regio-, and stereoselective Heck-Matsuda arylation of allylic alcohols under mild conditions

Heck arylation with allylic alcohol is extremely challenging due to chemo-, regio-, and stereoselective scrambling. Here we report a mild protocol for the alcohol selective β- and α-arylation of allylic and cinnamyl alcohols respectively with aryldiazonium salts. The steric and electronic parameters of the alkene play a prominent role in the regioselectivity.

Copper-catalyzed oxidative alkenylation of C(sp3)-H bonds via benzyl or alkyl radical addition to β-nitrostyrenes

A new method for the preparation of (E)-β-alkylstyrene derivatives has been developed via the addition of a benzyl or alkyl radical to β-nitrostyrenes using di-tert-butyl peroxide (DTBP) as the oxidant in the presence of Cu powder catalyst. The C-H bonds in various toluene derivatives, ethers, alkanes and alcohols were successfully converted into C-C bonds to yield the corresponding (E)-β-alkylstyrene derivatives in moderate to good yields.

Facile synthesis of Z -alkenes via uphill catalysis

Catalytic access to thermodynamically less stable Z-alkenes has recently received considerable attention. These approaches have relied upon kinetic control of the reaction to arrive at the thermodynamically less stable geometrical isomer. Herein, we present an orthogonal approach which proceeds via photochemically catalyzed isomerization of the thermodynamic E-alkene to the less stable Z-isomer which occurs via a photochemical pumping mechanism. We consider two potential mechanisms. Importantly, the reaction conditions are mild, tolerant, and operationally simple and will be easily implemented.