191725-56-1

Upstream product

• 4009-98-7 (methoxymethyl)triphenylphosphonium chloride 
• 99-91-2 para-chloroacetophenone 

Downstream Products

• 126866-18-0 1-phenyl-2-(4-chlorophenyl)-propan-1-one 
• 75854-92-1 (p-chlorophenyl)-4 methyl-4 cyclohexene-2 one-1 
• 102877-35-0 2-(4-chlorophenyl)-propane-1,2-diol 

Relevant academic research and scientific papers

Palladium-Catalyzed Allenamide Carbopalladation/Allylation with Active Methine Compounds

A palladium-catalyzed allenamide carbopalladation/allylation with active methine compounds has been developed. Various indoles and isoquinolinones bearing a quaternary carbon center were achieved with good efficiency, a broad substrate scope and good functional group tolerance. This reaction underwent cascade oxidative addition, carbopalladation, and allylic alkylation, and two new C-C bonds were formed in one pot.

Palladium-catalyzed synthesis of α-aryl acetophenones from styryl ethers and aryl diazonium saltsviaregioselective Heck arylation at room temperature

Preparation of α-aryl acetophenones from styryl ethers and aryldiazonium salts is described. The reaction is catalyzed by palladium acetate at room temperature in the absence of ligand and base. The developed method is highly attractive in terms of reaction conditions, substrate scope, functional group tolerance and yields. Synthetic applications of the present method are demonstrated by preparing α-aryl indoles and 3-aryl isocoumarin from styryl ethers.

Nickel-Catalyzed Desymmetric Hydrogenation of Cyclohexadienones: An Efficient Approach to All-Carbon Quaternary Stereocenters

Nickel-catalyzed desymmetric hydrogenation has been achieved. With the Ni(OTf)2/(S,S)-Ph-BPE system, a series of ?,?-disubstituted cyclohexadienones were transformed to the corresponding cyclohexenones with a chiral all-carbon quaternary center at the γposition in high yields (92-98%) and excellent enantioselectivities (92%-99% ee). This catalytic system can also tolerate the desymmetric reaction of spirocarbocyclic cyclohexadienones to produce the corresponding cyclohexenones bearing a chiral spiro quaternary carbon with high yields (94%-98%) and ee values (96%-99% ee). Furthermore, this methodology provides an efficient and concise synthetic route to the intermediate of natural products cannabispirenones A and B.

Copper-catalyzed vinylogous aerobic oxidation of unsaturated compounds with air

A mild and operationally simple copper-catalyzed vinylogous aerobic oxidation of β,γ- and α,β-unsaturated esters is described. This method features good yields, broad substrate scope, excellent chemo- and regioselectivity, and good functional group tolerance. This method is additionally capable of oxidizing β,γ- and α,β-unsaturated aldehydes, ketones, amides, nitriles, and sulfones. Furthermore, the present catalytic system is suitable for bisvinylogous and trisvinylogous oxidation. Tetramethylguanidine (TMG) was found to be crucial in its role as a base, but we also speculate that it serves as a ligand to copper(II) triflate to produce the active copper(II) catalyst. Mechanistic experiments conducted suggest a plausible reaction pathway via an allylcopper(II) species. Finally, the breadth of scope and power of this methodology are demonstrated through its application to complex natural product substrates.

Rhodium-catalyzed asymmetric hydrogenation of β-branched enamides for the synthesis of β-stereogenic amines

Using a rhodium complex of a bisphosphine ligand (R)-SDP, β-branched simple enamides with a (Z)-configuration were hydrogenated to β-stereogenic amines in quantitative yields and with excellent enantioselectivities (88-96% ee).

Asymmetric Synthesis of Remote Quaternary Centers by Copper-Catalyzed Desymmetrization: An Enantioselective Total Synthesis of (+)-Mesembrine

Catalytic asymmetric syntheses of remote quaternary stereocenters have been developed by copper-catalyzed 1,4-hydrosilylation of ?,?-disubstituted cyclohexadienones. A variety of cyclohexenones have been synthesized in good yield and excellent enantioselectivity. Versatile 2-silyloxy diene intermediates bearing ?,?-disubstituted all carbon stereogenic centers can be isolated from the mild reaction conditions. The utility of this strategy is exemplified in a catalytic asymmetric total synthesis of (+)-mesembrine.

Pummerer Cyclization Revisited: Unraveling of Acyl Oxonium Ion and Vinyl Sulfide Pathways

Two viable pathways (vinyl sulfide and acyl oxonium ion) for the Pummerer cyclization have been unraveled that expand the reaction scope and capabilities. Use of Br?nsted-enhanced Lewis acidity was key to realization of the vinyl sulfide pathway, whereas selective complexation of the sulfur lone pair facilitated the unprecedented acyl oxonium ion pathway. Preliminary mechanistic investigations support these hypotheses. A range of substrates have been explored to understand the reaction parameters.

Dynamic kinetic asymmetric amination of alcohols: From a mixture of four isomers to diastereo- and enantiopure α-branched amines

The first dynamic kinetic asymmetric amination of alcohols via borrowing hydrogen methodology is presented. Under the cooperative catalysis by an iridium complex and a chiral phosphoric acid, α-branched alcohols that exist as a mixture of four isomers undergo racemization by two orthogonal mechanisms and are converted to diastereo- and enantiopure amines bearing adjacent stereocenters. The preparation of diastereo- and enantiopure 1,2-amino alcohols is also realized using this catalytic system.

The catalytic asymmetric α-benzylation of aldehydes

The first aminocatalyzed α-alkylation of α-branched aldehydes with benzyl bromides as alkylating agents has been developed. Using a sterically demanding proline derived catalyst, racemic α-branched aldehydes are reacted with alkylating agents in a DYKAT process to give the corresponding α-alkylated aldehydes with quaternary stereogenic centers in good yields and high enantioselectivities. A sterically demanding proline derivative promotes the first aminocatalyzed α-alkylation of α-branched aldehydes with benzyl bromides as alkylating agents. Racemic α-branched aldehydes react with alkylating agents in a DYKAT process to give the corresponding α-alkylated aldehydes with quaternary stereogenic centers in good yields and high enantioselectivities. Copyright

Design and synthesis of thiadiazoles and thiazoles targeting the Bcr-Abl T315I mutant: From docking false positives to ATP-noncompetitive inhibitors

(Figure Presented) Overcoming resistance: In an effort to optimize our previously identified dual Src/Abl hits, a new series of 1,3,4-thiadiazoles and 1,3-thiazoles were designed and synthesized, paying particular attention to the reduction of their lipophilicity and to the improvement of the affinity towards the drug-resistant T315I mutant. Compound 5 was identified as a promising allosteric inhibitor of the T315I mutant.