72782-48-0

Upstream product

• 593-60-2 Vinyl bromide 
• 77693-45-9 1-(p-tolyl)ethylmagnesium chloride 
• 622-97-9 1-ethenyl-4-methylbenzene 
• 74-85-1 ethene 
• 54636-56-5 3-bromo-1-p-tolyl-1-propene 
• 75-16-1 methylmagnesium bromide 
• 54636-56-5 (E)-1-(3-bromoprop-1-en-1-yl)-4-methylbenzene 
• 104-87-0 4-methyl-benzaldehyde 
• 58824-48-9 1-(4-methylphenyl)-2-propen-1-ol 
• 201230-82-2 carbon monoxide 
• 96000-21-4 (E)-p-methylcinnamyl chloride 

Downstream Products

• 4176-17-4 (R)-(-)-α-curcumene 
• 106035-79-4 (R)-3-(4-methylphenyl)-1-butanol 
• 104598-15-4 (R)-3-(4-methylphenyl)butanal 
• 1141-54-4 (R)-2-methyl-6-(4-methylphenyl)-2-hepten-4-one 
• 765916-52-7 (6R)-2-methyl-6-(p-tolyl)hept-2-en-4-ol 

Relevant academic research and scientific papers

Improvements and Applications of the Transition Metal-Free Asymmetric Allylic Alkylation using Grignard Reagents and Magnesium Alanates

Two new N-heterocyclic carbene (NHC) ligands have been synthesized and employed in the transition metal-free asymmetric allylic alkylation (AAA) mediated by Grignard reagents and magnesium alanates. The employment of these ligands showed high yields and improved regio- and enantioselectivity in the formation of tertiary and quaternary stereocenters. Moreover, the low catalyst loading (up to 0.3 mol%) and high scalability (up to 10 mmol) of this improved methodology provide a convenient access to biologically active compounds and synthetically valuable intermediates.

Copper-free asymmetric allylic alkylation with a grignard reagent: Design of the ligand and mechanistic studies

The Cu-free asymmetric allylic alkylation, catalysed by NHC, with Grignard reagents is reported on allyl bromide derivatives with good results. The enantioselectivity was quite homogeneous (around 85 % ee) on large and various substrates, regardless of the nature of the Grignard reagent. The formation of stereogenic quaternary centres was highly regioselective for both aliphatic and aromatic derivatives with good enantiomeric excess (up to 92 % ee). The methodology developed was found to be complementary with the Cu-catalysed version. Several new NHCs were tested with improved efficiency. In addition, mechanistic studies, using NMR spectroscopy, led to the discovery of the catalytically active species. Copyright

Application of supramolecular bidentate hybrid ligands in asymmetric hydroformylation

In this study we report a novel class of supramolecular bidentate hybrid ligands in which the two inequivalent phosphorus units and pyridine moieties are covalently attached to a chiral scaffold and the supramolecular interactions are used as a second handle to control the coordination sphere around the transition-metal centre. The coordination chemistry of these ligands was investigated under hydroformylation conditions by high-pressure NMR and IR spectroscopy, revealing the formation of a single active species in which the phosphane ligand is in the axial position and the phosphoramidite adopts the equatorial position. These ligands were applied in the asymmetric Rh-catalysed hydroformylation of styrene and para-substituted analogues. In these hydroformylation reactions, modification of the electronic and steric properties of the zinc(II)-templates appear to have a significant influence on the activity and selectivity of the catalysis. In particular, zinc(II)-templates bearing more electron-withdrawing substituents led to an increase in enantioselectivity.

Enantioselective hydrovinylation via asymmetric counteranion-directed ruthenium catalysis

The first Ru-catalyzed enantioselective hydrovinylation has been realized by using an asymmetric counteranion-directed catalysis strategy. Styrene derivatives react with ethylene in excellent yields and promising enantioselectivity using this approach. Th

Syntheses and applications of 2-phosphino-2′-alkoxy-1,1′- binaphthyl ligands. Development of a working model for asymmetric induction in hydrovinylation reactions

Among the handful of monophosphine ligands that effect asymmetric hydrovinylation of vinylarenes, 2-diphenylphosphino-2′-methoxy-1,1′- binaphthyl (MOP) is among the most accessible. Addition of a methyl group at the 3′-position of this ligand significantl

Palladium-catalyzed asymmetric hydrovinylation under mild conditions using monodentate chiral spiro phosphoramidite and phosphite ligands

Palladium complexes of chiral spiro phosphoramidite and phosphite ligands are effective catalysts in the asymmetric hydrovinylation of vinylarenes with ethylene. The hydrovinylation products were obtained in modest selectivity with enantioselectivities up to 92% ee. The structures of the palladium catalysts have been analyzed by X-ray diffraction. The active catalyst contained one monodentate ligand. A kinetic resolution accompanied the isomerization of the hydrovinylation product in the reaction.

Copper catalyzed enantioselective allylic substitution by MeMgX

Methyl Grignard undergoes highly regio (>90/10) and enantioselective (ee 91-96%) copper catalyzed allylic substitution on cinnamyl-type chlorides. CuBr (3%) and 3.3% of a chiral phosphoramidite ligand are sufficient for a complete reaction. The synthesis of a precursor of (+)-Naproxen is described. The reaction can be extended to alkyl substituted allylic chlorides (ee 72%).

Chiral benzyl centers through asymmetric catalysis. A three-step synthesis of (R)-(-)-α-curcumene via asymmetric hydrovinylation

(Chemical Equation Presented) A three-step, two-pot procedure involving asymmetric hydrovinylation followed by Suzuki-Miyaura reaction represents by far the shortest synthesis of this popular bisabolane. Other applications for the synthesis of similar com

Fine-tuning monophosphine ligands for enhanced enantioselectivity. Influence of chiral hemilabile pendant groups

C2-Symmetric P-(2-X-aryl)-2,5-dialkylphospholanes (X = dioxolan-2-yl or dioxan-2-yl), designed on the basis of a working model for asymmetric induction, are effective ligands for the Ni(II)-catalyzed asymmetric hydrovinylation of styrenes. Excellent yields (>99%), selectivities for the desired 3-arylbutenes (>99%), high S/C ratios (>1200), and ee's (up to 91%) have been realized for a number of prototypical vinylarenes. In the dioxolane series, the selectivity depends on the configuration of the C 4 and C5 carbons.