77693-46-0

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 
• 96000-21-4 (E)-p-methylcinnamyl chloride 
• 75-16-1 methylmagnesium bromide 
• 1394035-47-2 (2E)-but-2-en-1-yl 4-(trifluoromethyl)phenyl ether 
• 5720-05-8 4-methylphenylboronic acid 
• 201230-82-2 carbon monoxide 
• 54636-56-5 3-bromo-1-p-tolyl-1-propene 
• 58824-48-9 1-(4-methylphenyl)-2-propen-1-ol 
• 104-87-0 4-methyl-benzaldehyde 
• 54636-56-5 (E)-1-(3-bromoprop-1-en-1-yl)-4-methylbenzene 

Relevant academic research and scientific papers

Total Synthesis of (+)-Erogorgiaene and the Pseudopterosin A?F Aglycone via Enantioselective Cobalt-Catalyzed Hydrovinylation

Due to their pronounced bioactivity and limited availability from natural resources, metabolites of the soft coral Pseudopterogorgia elisabethae, such as erogorgiaene and the pseudopterosines, represent important target molecules for chemical synthesis. We have now developed a particularly short and efficient route towards these marine diterpenes exploiting an operationally convenient enantioselective cobalt-catalyzed hydrovinylation as the chirogenic step. Other noteworthy C?C bond forming transformations include diastereoselective Lewis acid-mediated cyclizations, a Suzuki coupling and a carbonyl ene reaction. Starting from 4-methyl-styrene the anti-tubercular agent (+)-erogorgiaene (>98 % ee) was prepared in only 7 steps with 46 % overall yield. In addition, the synthesis of the pseudopterosin A aglycone was achieved in 12 steps with 30 % overall yield and, surprisingly, was found to exhibit a similar anti-inflammatory activity (inhibition of LPS-induced NF-κB activation) as a natural mixture of pseudopterosins A?D or iso-pseudopterosin A, prepared by β-D-xylosylation of the synthetic aglycone.

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.

Rhodium-catalyzed asymmetric coupling reaction of allylic ethers with arylboronic acids

An asymmetric allylic substitution of simple allylic ethers with arylboronic acids in the presence of a rhodium(I)/(R)-DTBM-SEGPHOS catalyst has been developed. The reactions proceeded smoothly at room temperature to give the corresponding branch products with excellent regioselectivities and good to excellent enantioselectivities.

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.

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