55177-37-2

Upstream product

• 646-05-9 pent-1-en-3-yne 
• 85363-29-7 3-(trimethylsilyl)-2-phenyl-2-hydroxy-4-pentene 
• 75749-88-1 (1-Methyl-cyclobut-2-enyl)-benzene 
• 107-18-6 allyl alcohol 
• 98-86-2 acetophenone 
• 20628-90-4 2-Allyl-1,3-dimethyl-[1,3,2]diazaphospholidine 2-oxide 
• 53915-69-8 allenyltributylstannane 
• 1196-67-4 (Z)-3-Phenyl-but-2-en-1-al 
• 1779-49-3 Methyltriphenylphosphonium bromide 
• 1196-67-4 3-phenyl-2-butenal 
• 1067-87-4 Diethyl allylphosphonate 
• 4743-74-2 2-phenylpent-4-en-2-ol 
• 57501-29-8 4-chloro-4-phenyl-pent-1-ene 

Downstream Products

• 958456-97-8 (2E,6Z)-ethyl 3-methyl-7-phenylocta-2,6-dienoate 

Relevant academic research and scientific papers

CONTROLLED REVERSAL OF CHEMOSELECTIVITY IN REACTIONS OF ALLYLTITANIUM ATE COMPLEXES WITH CARBONYL COMPOUNDS

Allyltitanium ate complexes react either aldehyde- or ketone-selectively, depending upon the nature of the ligands at titanium.

Photoinduced Copper-Catalyzed Asymmetric C-O Cross-Coupling

The construction of carbon-heteroatom bonds is one of the most active areas of research in organic chemistry because the function of organic molecules is often derived from the presence of heteroatoms. Although considerable advances have recently been achieved in radical-involved catalytic asymmetric C-N bond formation, there has been little progress in the corresponding C-O bond-forming processes. Here, we describe a photoinduced copper-catalyzed cross-coupling of readily available oxime esters and 1,3-dienes to generate diversely substituted allylic esters with high regio- and enantioselectivity (>75 examples; up to 95% ee). The reaction proceeds at room temperature under excitation by purple light-emitting diodes (LEDs) and features the use of a single, earth-abundant copper-based chiral catalyst as both the photoredox catalyst for radical generation and the source of asymmetric induction in C-O coupling. Combined experimental and density functional theory (DFT) computational studies suggest the formation of π-allylcopper complexes from redox-active oxime esters as bifunctional reagents and 1,3-dienes through a radical-polar crossover process.

Efficient one-to-one coupling of easily available 1,3-dienes with carbon dioxide

An efficient one-to-one coupling reaction of atmospheric pressure carbon dioxide with 1,3-dienes is realized for the first time through PSiP-pincer type palladium-catalyzed hydrocarboxylation. The reaction is applicable to various 1,3-dienes including easily available chemical feedstock such as 1,3-butadiene and isoprene. This protocol affords a highly useful method for the synthesis of β,γ-unsaturated carboxylic acid derivatives from CO2.

Competitive inhibition of aristolochene synthase by phenyl-substituted farnesyl diphosphates: Evidence of active site plasticity

Analogues of farnesyl diphosphate (FPP, 1) containing phenyl substituents in place of methyl groups have been prepared in syntheses that feature use of a Suzuki-Miyaura reaction as a key step. These analogues were found not to act as substrates of the sesquiterpene cyclase aristolochene synthase from Penicillium roqueforti (AS). However, they were potent competitive inhibitors of AS with KI-values ranging from 0.8 to 1.2 M. These results indicate that the diphosphate group contributes the largest part to the binding of the substrate to AS and that the active sites of terpene synthases are sufficiently flexible to accommodate even substrate analogues with large substituents suggesting a potential way for the generation of non-natural terpenoids. Molecular mechanics simulations of the enzyme bound inhibitors suggested that small changes in orientations of active site residues and subtle alterations of the conformation of the backbones of the inhibitors are sufficient to accommodate the phenyl-farnesyl-diphosphates. This journal is The Royal Society of Chemistry.

A new ruthenium-catalyzed hydrogen-transfer reaction: Transformation of 3-benzyl but-1-ynyl ethers into 1,3-dienes and benzaldehyde

(Chemical Equqtion Presentation) We report a ruthenium-catalyzed reaction for various 3-benzyl but-1-ynyl ethers with suitable functionalities. Treatment of these substrates with TpRu(PPh3)(CH3CN)2PF6 (8.0 mol %

AgAsF6 as safe alternative to AgClO4 for generating cationic zirconocene species: Utilities in Lewis acid-promoted selective C---C bond forming reactions

For generating cationic zirconocene species that are useful for organic synthesis, AgAsF6 proved to be an efficient catalyst that serves as a safe alternative to AgClO4. Scope and limitation is discussed on this new catalyst in the processes including (1) alkyl/alkenyl transfer reaction from organozirconocene chloride to aldehyde, (2) two- and four-carbon homologation of aldehyde, (3) dual synthetic methods of 1,3-dienes from aldehydes/ketones via 1,3-bimetallic species, and (4) three-component alkylative cycloaddition via o-quinodimethane species.

EFFICIENT OLEFINATION WITH α-ALKYL CYCLIC PHOSPHONAMIDES

A variety of acyclic and cyclic aldehydes and ketones can be converted into the corresponding alkylidene, benzylidene and methoxycarbonyl alkylidene derivatives by treatment with 1,3,2-diazaphospholidine-2-alkyl-1,3-dimethyl 2-oxides (α-alkyl cyclic phosphonamides) under mild conditions.This olefination method is particularly useful in the case of enolizable carbonyl compounds.

Palladium-catalyzed carbonyl allylation by allylic alcohols with SnCl2

Allylic alcohols can be applied to carbonyl allylation via the formation of π-allylpalladium complexes, using palladium as catalyst and SnCl2 as a reducing agent. This reaction has chemoselectivity: The reactivity order of allylating agents is allylic carbonate > allylic alcohol > allylic acetate, and that of carbonyl compounds is aldehyde > ketone. High regioselcction was observed in polar solvents such as DMF, DMI, and DMSO; carbonyl compounds apparently attacked the more substituted allylic position of π-allylpalladium complexes to afford only one regioisomer. Diastereocontrol in the carbonyl allylation of aromatic aldehydes by (E)-2-butenol was achieved by the choice of polar solvents; use of DMSO at 25 °C led to syn selection, while anti selection was found at -10 °C in THF. The addition of H2O in any solvent accelerated the carbonyl allylation and enhanced both regioselectivity and the diastereoselectivity. Anti selection in DMF, DMI, and THF-H2O can be explained by the chair form of the six-membered cyclic transition state, while syn selection in DMSO allows us to propose an acyclic antiperiplanar transition state. An NMR spectroscope investigation demonstrated that the actual allylating agent in dry medium was allyltrichlorotin: 1H, 13C, and 119Sn NMR spectra of the reaction of allyl alcohol with PdCl2(PhCN)2-SnCl2 in DMF-d7. corresponded to those of the reaction of allyl chloride with PdCl2(PhCN)2-SnCl2 in DMF-d7.

A Novel Intramolecular Cyclisation of Titanocene Vinylidene Complexes: Formation of Bicyclic Titanacyclo-butanes and -butenes

The intramolecular addition of a titanocene vinylidene complex formed by dechlorodimethylalumination of a 1-dimethylalumino-1-bis(η5-cyclopentadienyl)chlorotitano-alkene to an unactivated alkene or alkyne affords bicyclic titanacyclobutanes or titanacyclobutenes.

Stereoselective Addition of Organotitanium Reagents to Carbonyl Compounds

Titanation of alkyllithium or -magnesium compounds using ClTi(OR)3 results in reagents which show markedly increased diastereofacial selectivity (80 - 90percent) in reactions with α-chiral aldehydes or ketones.Titanation is also the method of choice in Grignard-type additions to substituted cyclohexanones; CH3Ti(OCHMe2)3 (6a) adds predominantly from the equatorial direction, while allyltitanium reagents 11b and 12 show axial preference.Crotyltitanium compounds react with carbonyl compounds to afford primarily adducts having anti-configuration, a process which is of particular value in case of ketones (anti/syn ratios up to 99:1).Titanation of (trimethylsilyl)allyllithium (48) with Ti(OCHMe2)4 reverses regioselectivity in reactions with aldehydes and ketones, β-hydroxy silanes 50 being the only observed products.These have anti-configuration and can be converted either into Z- or E-dienes using the Peterson elimination under basic or acidic conditions, respectively.