51431-73-3

Upstream product

• 1530-32-1 ethyltriphenylphosphonium bromide 
• 100-06-1 1-(4-methoxyphenyl)ethanone 
• 925-90-6 ethylmagnesium bromide 
• 21758-19-0 4-(but-1-en-2-yl)anisole 
• 87931-49-5 3-p-methoxypent-3-enoic acid 
• 122948-71-4 1-<α-(p-tolylsulfonyl)ethyl>-4-methoxybenzene 
• 38454-62-5 (E)-2-(4-methoxyphenyl)but-2-ene 
• 4518-65-4 (1-methoxyprop-1-en-1-yl)benzene 
• 137628-39-8 (S)-2-(4-methoxyphenyl)-2-butanol 
• 30068-21-4 2-(4-methoxyphenyl)-1-methyl-2-propanol 
• 10467-10-4 ethylmagnesium iodide 
• 121-97-1 4-Methoxypropiophenone 
• 52178-73-1 1-(2,2-dibromo-1-methylcyclopropyl)-4-methoxybenzene 
• 191725-57-2 1-methoxy-4-(1-methoxyprop-1-en-2-yl)benzene 

Downstream Products

• 35144-34-4 erythro-3-(4-methoxyphenyl)butan-2-ol 
• 38454-63-6 Z-2-(4-methoxyphenyl)-2-butene 
• 51431-74-4 p-(2,2-dichloro-1,3-dimethylcyclopropyl)anisole 
• 4917-90-2 1-sec-butyl-4-methoxybenzene 
• 4132-48-3 1-methoxy-4-(1-methylethyl)benzene 
• 21758-19-0 4-(but-1-en-2-yl)anisole 
• 38454-62-5 (E)-2-(4-methoxyphenyl)but-2-ene 
• 929030-72-8 (E)-1-methoxy-4-(1-methoxyprop-1-en-2-yl)benzene 
• 100-06-1 1-(4-methoxyphenyl)ethanone 

Relevant academic research and scientific papers

Titanocene(III)-Catalyzed Precision Deuteration of Epoxides

We describe a titanocene(III)-catalyzed deuterosilylation of epoxides that provides β-deuterated anti-Markovnikov alcohols with excellent D-incorporation, in high yield, and often excellent diastereoselectivity after desilylation. The key to the success of the reaction is a novel activation method of Cp2TiCl2 and (tBuC5H4)2TiCl2 with BnMgBr and PhSiD3 to provide [(RC5H4)2Ti(III)D] without isotope scrambling. It was developed after discovering an off-cycle scrambling with the previously described method. Our precision deuteration can be applied to the synthesis of drug precursors and highlights the power of combining radical chemistry with organometallic catalysis.

Iron-Catalyzed Highly Enantioselective Hydrogenation of Alkenes

Here, we reported for the first time an iron-catalyzed highly enantioselective hydrogenation of minimally functionalized 1,1-disubstituted alkenes to access chiral alkanes with full conversion and excellent ee. A novel chiral 8-oxazoline iminoquinoline ligand and its iron complex have been designed and synthesized. This protocol is operationally simple by using 1 atm of hydrogen gas and shows good functional group tolerance. A primary mechanism has been proposed by the deuterium-labeling experiments.

Palladium-Catalyzed Markovnikov Hydroaminocarbonylation of 1,1-Disubstituted and 1,1,2-Trisubstituted Alkenes for Formation of Amides with Quaternary Carbon

Hydroaminocarbonylation of alkenes is one of the most promising yet challenging methods for the synthesis of amides. Herein, we reported the development of a novel and effective Pd-catalyzed Markovnikov hydroaminocarbonylation of 1,1-disubstituted or 1,1,2-trisubstituted alkenes with aniline hydrochloride salts to afford amides bearing an α quaternary carbon. The reaction makes use of readily available starting materials, tolerates a wide range of functional groups, and provides a facile and straightforward approach to a diverse array of amides bearing an α quaternary carbon. Mechanistic investigations suggested that the reaction proceeded through a palladium hydride pathway. The hydropalladation and CO insertion are reversible, and the aminolysis is probably the rate-limiting step.

Iron Catalyzed Isomerization of α-Alkyl Styrenes to Access Trisubstituted Alkenes

Stereoselective isomerization of α-alkyl styrenes is accomplished using a new iron catalyst supported by phosphine-pyridine-oxazoline (PPO) ligand. The protocol provides an atom-efficient and operationally simple approach to trisubstituted alkenes in high

Intermolecular Carbonyl–olefin Metathesis with Vinyl Ethers Catalyzed by Homogeneous and Solid Acids in Flow

The carbonyl–olefin metathesis reaction has experienced significant advances in the last seven years with new catalysts and reaction protocols. However, most of these procedures involve soluble catalysts for intramolecular reactions in batch. Herein, we show that recoverable, inexpensive, easy to handle, non-toxic, and widely available simple solid acids, such as the aluminosilicate montmorillonite, can catalyze the intermolecular carbonyl–olefin metathesis of aromatic ketones and aldehydes with vinyl ethers in-flow, to give alkenes with complete trans stereoselectivity on multi-gram scale and high yields. Experimental and computational data support a mechanism based on a carbocation-induced Grob fragmentation. These results open the way for the industrial implementation of carbonyl–olefin metathesis over solid catalysts in continuous mode, which is still the origin and main application of the parent alkene–alkene cross-metathesis.

Cobalt(II)-Catalyzed Stereoselective Olefin Isomerization: Facile Access to Acyclic Trisubstituted Alkenes

Stereoselective synthesis of trisubstituted alkenes is a long-standing challenge in organic chemistry, due to the small energy differences between E and Z isomers of trisubstituted alkenes (compared with 1,2-disubstituted alkenes). Transition metal-catalyzed isomerization of 1,1-disubstituted alkenes can serve as an alternative approach to trisubstituted alkenes, but it remains underdeveloped owing to issues relating to reaction efficiency and stereoselectivity. Here we show that a novel cobalt catalyst can overcome these challenges to provide an efficient and stereoselective access to a broad range of trisubstituted alkenes. This protocol is compatible with both mono- and dienes and exhibits a good functional group tolerance and scalability. Moreover, it has proven to be a useful tool to construct organic luminophores and a deuterated trisubstituted alkene. A preliminary study of the mechanism suggests that a cobalt-hydride pathway is involved in the reaction. The high stereoselectivity of the reaction is attributed to both a π-πstacking effect and the steric hindrance between substrate and catalyst.

Cobalt-Catalyzed Migrational Isomerization of Styrenes

An efficient cobalt-catalyzed migrational isomerization of styrenes was developed using the thiazoline iminopyridine (TIP) ligand. This reaction is operationally simple and atom-economical using readily available starting materials to access trisubstituted alkenes. Even when using a 0.1 mol % catalyst loading, the reaction could be conducted in neat and completed in 1 h with excellent conversion and high E stereoselectivity.

Method for stereoselective synthesis of (E)-trisubstituted olefin

Belonging to the technical field of metal catalytic synthesis, the invention discloses a method for stereoselective synthesis of (E)-trisubstituted olefin. The method includes: taking 1, 1-disubstituted olefin as the raw material, and adopting a combination of CoX2 and PAO ligand as the catalyst; and in the presence of an activating reagent, carrying out reaction for 0.5min-48h at a temperature ranging from -30DEG C to 80DEG C to prepare (E)-trisubstituted olefin. Compared with the prior art, the method has the advantages of more economical, efficient and environment-friendly catalyst, good tolerance of the reaction functional group, mild reaction conditions, simple operation, no need for participation of additional reagents, and atom economy of 100%. In addition, the reaction has no needof any other toxic transition metal (like ruthenium, rhodium, palladium, etc.) salt, therefore the method has great practical application value in pharmaceutical and food chemical industry.

Aminoxyl-Catalyzed Electrochemical Diazidation of Alkenes Mediated by a Metastable Charge-Transfer Complex

We report the development of a new aminoxyl radical catalyst, CHAMPO, for the electrochemical diazidation of alkenes. Mediated by an anodically generated charge-transfer complex in the form of CHAMPO-N3, radical diazidation was achieved across a broad scope of alkenes without the need for a transition metal catalyst or a chemical oxidant. Mechanistic data support a dual catalytic role for the aminoxyl serving as both a single-electron oxidant and a radical group transfer agent.

Regioselective Diboron-Mediated Semireduction of Terminal Allenes

A method for the regioselective reduction of the terminal double bond of 1,1-disubstituted allenes has been developed. In the presence of a palladium catalyst, tetrahydroxydiboron and stoichiometric water, allene semireduction proceeds in high yield to afford Z-alkenes selectively.