15325-54-9

Upstream product

• 109-72-8 n-butyllithium 
• 622-25-3 1-(2-chlorovinyl)benzene 
• 103-64-0 bromostyrene 
• 4471-05-0 1-phenylhexan-1-ol 
• 71-43-2 benzene 
• 16619-61-7 1-phenyl-2-phenylthioethene 
• 592-41-6 1-hexene 
• 62-38-4 phenylmercuric acetate 
• 35843-79-9 (6-chloro-1-hexyn-1-yl)benzene 
• 16664-48-5 6-bromo-1-phenyl-1-hexyne 
• 693-25-4 n-pentylmagnesium bromide 
• 100-52-7 benzaldehyde 
• 693-03-8 n-butyl magnesium bromide 
• 588-73-8 (Z)-β-bromostyrene 

Downstream Products

• 1743-30-2 2-Hydrazino-1-phenyl-hexan 
• 1536240-42-2 (1-phenylhexan-2-yl)phosphinic acid 

Relevant academic research and scientific papers

Highly chemo- and stereoselective Fe-catalyzed alkenylation of organomanganese reagents

Organomanganese chlorides react with alkenyl iodides, bromides and chlorides in the presence of 3% Fe(acac)3. The reaction takes place under very mild conditions (THF-NMP, rt, 1h) to afford the substituted olefin in excellent yields with a high stereo- and chemoselectivity. Thus an unprotected keto alkenyl chloride selectively gives the corresponding keto olefin. From a preparative point of view, this procedure is the first real alternative to the Pd- and Ni-cross coupling reaction used until now.

A rearrangement to a zirconium-alkenylidene in the insertion of dihalocarbenoids and acetylides into zirconacycles

(Chemical Equation Presented) Sequential insertion of 1-lithio-1,1- dihaloalkanes and lithium acetylides into zirconacyclopentenes and -pentanes affords complex bicyclo[3.3.0]octenes and bicyclo[3.3.0]octanes through a novel rearrangement of a zirconium-a

Homolytic allylation of vinyl iodides with allylstannanes

In the presence of AIBN or Et3B, a variety of vinyl iodides reacted with allylstannanes bearing an electron-withdrawing group at the β-position to afford 1,4-dienes in moderate to good yields. The allylation showed high stereoselectivity when t

A facile stereoselective synthesis of (E)-1,2-disubstituted vinylic selenides via hydromagnesiation of alkylarylacetylenes

Hydromagnesiation of alkylarylacetylenes 1 in diethyl ether gave (E)-α-arylvinyl Grignard reagents 2, which reacted with arylselenenyl bromides 3 in THF to afford stereoselectively (E)-1,2-disubstituted vinylic selenides 4 in good yields.

Ir-Catalyzed Remote Functionalization by the Combination of Deconjugative Chain-Walking and C-H Activation Using a Transient Directing Group

An Ir-catalyzed reaction of N-benzylideneanilines with functionalized alkenes such as α,β-unsaturated esters gave ortho-substituted benzaldehyde derivatives with a functional group at the remote position after acidic treatment. The present transformation

An Amine-Assisted Ionic Monohydride Mechanism Enables Selective Alkyne cis-Semihydrogenation with Ethanol: From Elementary Steps to Catalysis

The selective synthesis of Z-alkenes in alkyne semihydrogenation relies on the reactivity difference of the catalysts toward the starting materials and the products. Here we report Z-selective semihydrogenation of alkynes with ethanol via a coordination-induced ionic monohydride mechanism. The EtOH-coordination-driven Cl- dissociation in a pincer Ir(III) hydridochloride complex (NCP)IrHCl (1) forms a cationic monohydride, [(NCP)IrH(EtOH)]+Cl-, that reacts selectively with alkynes over the corresponding Z-alkenes, thereby overcoming competing thermodynamically dominant alkene Z-E isomerization and overreduction. The challenge for establishing a catalytic cycle, however, lies in the alcoholysis step; the reaction of the alkyne insertion product (NCP)IrCl(vinyl) with EtOH does occur, but very slowly. Surprisingly, the alcoholysis does not proceed via direct protonolysis of the Ir-C(vinyl) bond. Instead, mechanistic data are consistent with an anion-involved alcoholysis pathway involving ionization of (NCP)IrCl(vinyl) via EtOH-for-Cl substitution and reversible protonation of Cl- ion with an Ir(III)-bound EtOH, followed by β-H elimination of the ethoxy ligand and C(vinyl)-H reductive elimination. The use of an amine is key to the monohydride mechanism by promoting the alcoholysis. The 1-amine-EtOH catalytic system exhibits an unprecedented level of substrate scope, generality, and compatibility, as demonstrated by Z-selective reduction of all alkyne classes, including challenging enynes and complex polyfunctionalized molecules. Comparison with a cationic monohydride complex bearing a noncoordinating BArF- ion elucidates the beneficial role of the Cl- ion in controlling the stereoselectivity, and comparison between 1-amine-EtOH and 1-NaOtBu-EtOH underscores the fact that this base variable, albeit in catalytic amounts, leads to different mechanisms and consequently different stereoselectivity.

Ligand-free (: Z)-selective transfer semihydrogenation of alkynes catalyzed by in situ generated oxidizable copper nanoparticles

Herein, we present (Z)-selective transfer semihydrogenation of alkynes based on in situ generated CuNPs in the presence of hydrogen donors, such as ammonia-borane and a green protic solvent. This environmentally friendly method is characterized by operational simplicity combined with high stereo- and chemoselectivity and functional group compatibility. Auto-oxidation of CuNPs after the completion of a semihydrogenation reaction results in the formation of a water-soluble ammonia complex, so that the catalyst may be reused several times by simple phase-separation with no need for any special regeneration processes. Formed NH4B(OR)4 can be easily transformed back into ammonia-borane or into boric acid. In addition, a one-pot tandem sequence involving a Suzuki reaction followed by semihydrogenation was presented, which allows minimization of chemical waste production.

A simple and efficientin situgenerated copper nanocatalyst for stereoselective semihydrogenation of alkynes

Development of a simple, effective, and practical method for (Z)-selective semihydrogenation of alkynes has been considered necessary for easy-to-access applications at organic laboratory scales. Herein, (Z)-selective semihydrogenation of alkynes was achieved using a copper nanocatalyst which was generatedin situsimply by adding ammonia borane to an ethanol solution of copper sulfate. Different types of alkynes including aryl-aryl, aryl-alkyl, and aliphatic alkynes were selectively reduced to (Z)-alkenes affording up to 99% isolated yield. The semihydrogenation of terminal alkynes to alkenes and gram-scale applications were also reported. In addition to eliminating catalyst preparation, the proposed approach is simple and practical and serves as a suitable alternative method to the conventional Lindlar catalyst.

Dinuclear cobalt complex-catalyzed stereodivergent semireduction of alkynes: Switchable selectivities controlled by H2O

Catalytic semireduction of internal alkynes to alkenes is very important for organic synthesis. Although great success has been achieved in this area, switchable Z/E stereoselectivity based on a single catalyst for the semireduction of internal alkynes is a longstanding challenge due to the multichemo- and stereoselectivity, especially based on less-expensive earth-abundant metals. Herein, we describe a switchable semireduction of alkynes to (Z)- or (E)-alkenes catalyzed by a dinuclear cobalt complex supported by a macrocyclic bis pyridyl diimine (PDI) ligand. It was found that cis-reduction of the alkyne occurs first and the Z-E alkene stereoisomerization process is formally controlled by the amount of H2O, since the concentration of H2O may influence the catalytic activity of the catalyst for isomerization. Therefore, this protocol provides a facile way to switch to either the (Z)- or (E)-olefin isomer in a single transformation by adjusting the amount of water.

Recyclable and reusable PdCl2(PPh3)2/PEG-400/H2O system for the hydrophenylation of alkynes with sodium tetraphenylborate

A stable and efficient PdCl2(PPh3)2/PEG-400/H2O catalytic system for the hydrophenylation reaction of alkynes has been developed. In the presence of 3 mol% PdCl2(PPh3)2 and 2 equiv. of HOAc, the hydrophenylation of both terminal and internal alkynes with sodium tetraphenylborate proceeded smoothly in a mixture of PEG-400 and water at room temperature or 50 °C to afford a variety of phenyl-substituted alkenes in moderate to high yields. The isolation of the products was easily performed by extraction with petroleum ether, and the PdCl2(PPh3)2/PEG-400/H2O system could be readily recycled and reused six times without apparent loss of catalytic activity.