123494-30-4

Upstream product

• 97-94-9 triethyl borane 
• 706-08-1 trans-1-(4-fluorophenyl)-2-nitro-ethene 
• 97-93-8 triethylaluminum 
• 96-10-6 diethylaluminium chloride 
• 459-46-1 4-Fluorobenzyl bromide 
• 2248-13-7 1-(but-3-en-1-yl)-4-fluorobenzene 
• 620-97-3 1-(4-fluorophenyl)butan-2-one 
• 5153-69-5 4-fluoro-β-nitrostyrene 
• 1115-99-7 triethyl gallium 
• 137224-83-0 Selenophosphoric acid Se-[1-(4-fluoro-phenyl)-2-oxo-butyl] ester O,O'-dimethyl ester 
• 137224-96-5 Thiophosphoric acid S-[1-(4-fluoro-phenyl)-2-oxo-butyl] ester O,O'-dimethyl ester 

Downstream Products

• 111496-39-0 [4-(4-fluorophenyl)butyl]phosphinic acid, 1-adamantanamine salt 

Relevant academic research and scientific papers

Selecting double bond positions with a single cation-responsive iridium olefin isomerization catalyst

The catalytic transposition of double bonds holds promise as an ideal route to alkenes of value as fragrances, commodity chemicals, and pharmaceuticals; yet, selective access to specific isomers is a challenge, normally requiring independent development of different catalysts for different products. In this work, a single cation-responsive iridium catalyst selectively produces either of two different internal alkene isomers. In the absence of salts, a single positional isomerization of 1-butene derivatives furnishes 2-alkenes with exceptional regioselectivity and stereoselectivity. The same catalyst, in the presence of Na+, mediates two positional isomerizations to produce 3-alkenes. The synthesis of new iridium pincer-crown ether catalysts based on an aza-18-crown-6 ether proved instrumental in achieving cation-controlled selectivity. Experimental and computational studies guided the development of a mechanistic model that explains the observed selectivity for various functionalized 1-butenes, providing insight into strategies for catalyst development based on noncovalent modifications.

Controllable Isomerization of Alkenes by Dual Visible-Light-Cobalt Catalysis

We report herein that thermodynamic and kinetic isomerization of alkenes can be accomplished by the combination of visible light with Co catalysis. Utilizing Xantphos as the ligand, the most stable isomers are obtained, while isomerizing terminal alkenes over one position can be selectively controlled by using DPEphos as the ligand. The presence of the donor–acceptor dye 4CzIPN accelerates the reaction further. Transformation of exocyclic alkenes into the corresponding endocyclic products could be efficiently realized by using 4CzIPN and Co(acac)2 in the absence of any additional ligands. Spectroscopic and spectroelectrochemical investigations indicate CoI being involved in the generation of a Co hydride, which subsequently adds to alkenes initiating the isomerization.

Free radical reactions to generate alkenes and/or ionic reactions to generate hydroximoyl chlorides when β-nitrostyrenes react with triethylaluminium or diethylaluminium chloride

β-Nitrostyrenes 1 react with triethylaluminium or diethylaluminium chloride in diethyl ether solution and under nitrogen or argon to generate the alkenes 2 and the hydroximoyl chlorides 3 after work-up with ice-cold, cone, hydrochloric acid. The formation of the alkenes 2 is proposed to be a free-radical reaction via NO2/alkyl substitution since the yields of the alkenes 2 are increased in the presence of benzoyl peroxide (Bz2O2) and decreased in the presence of galvinoxyl. Only the alkenes 2 are produced with a high stereoselectivity for the E isomers when β-nitrostyrenes react with triethylaluminium in the presence of one to two equivalents of Bz2O2 as free-radical initiator. The mechanism of the generation of the hydroximoyl chlorides 3 is proposed to proceed through a 1,4-addition pathway to produce nitronates A, then the protonated nitronates B or the nitroso cations C are trapped by chloride ion to form the final products. The yields of compounds 3 are also improved by the presence of Lewis acids such as MgCl2. Medium to high yields of the hydroximoyl chlorides 3 and traces or low yields of the alkenes 2 are generated when triethylaluminium or diethylaluminium chloride react with β-nitrostyrenes in the presence of three equivalents of MgCl2 under argon.

Free-Radical Reactions of Trialkylboranes with β-Nitrostyrenes to Generate Alkenes

β-Nitrostyrenes 1 react with trialkylboranes under a nitrogen atmosphere to generate high yields of alkenes 2. The mechanism is proposed to be a free-radical reaction via NO2/alkyl substitution since the reaction is stimulated by the presence of a trace of oxygen in the nitrogen or tert-butyl peroxide or by photolysis and is retarded or inhibited by the addition of galvinoxyl to the solution.

An unexpected reaction between 2-aryl-1-nitro-1-alkenes and trialkylgallium compounds

A novel reaction between 2-aryl-1-nitro-1-alkenes and trialkylgallium compound via NO2/alkyl substitution is found, and a possible mechanism is proposed.

A NEW STRATEGY FOR THE STEREOSELECTIVE SYNTHESIS OF OLEFINS

Highly stereoselective conversion of ketones into (Z)-olefins, via intermediate S-(β-oxoalkyl)thiophosphates and their seleno analogues is described.

ORALLY ACTIVE PHOSPHONYL HYDROXYACYL PROLINES

This invention is directed to orally active antihypertensive agents of the formula STR1 wherein R 1 is certain alkyl or aralkyl groups.