51086-44-3

Upstream product

• 934-85-0 styrene-d2 
• 103-82-2 phenylacetic acid 
• 1076-07-9 2,2-dideuterio-2-phenyl-acetic acid 
• 122-78-1 phenylacetaldehyde 
• 51086-45-4 2,2-dideuterio-2-phenyl-ethanol 

Downstream Products

• 1283741-97-8 1-phenyl[2H₂]methyl-1,2,3,4-tetrahydroisoquinoline-6,7-diol 
• 60604-09-3 3-phenylpropane-3,3-d₂ 
• 93250-19-2 threo-4,4-dideutero-1,4-diphenyl-3-hydroxy-2-methyl-1-butanone 
• 93250-19-2 erythro-4,4-dideutero-1,4-diphenyl-3-hydroxy-2-methyl-1-butanone 
• 116503-63-0 1,4-diphenyl-2-butene-1,1,4,4-d4 

Relevant academic research and scientific papers

Nickel-Catalyzed Allylic C(sp2)–H Activation: Stereoselective Allyl Isomerization and Regiospecific Allyl Arylation of Allylarenes

Stereoselective allyl isomerization and regiospecific allyl arylation reactions of allylarenes with a catalytic system comprising nickel(II) with an aryl Grignard reagent were studied. Both reactions are triggered by allylic internal C(sp2)–H activation by in-situ-formed Ni0, which is inserted into the C–H bond at the 2-position of the allyl moiety without a directing group. The isomerization of allylarene to 1-propenylarene favors the E isomer and proceeds with quantitative conversion. The arylation takes place through oxidative cross-coupling of allylarenes with excess Grignard reagent. It occurs regiospecifically at the position of C(sp2)–H activation and represents a new method for the synthesis of 1,1-disubstituted olefins. The results of deuterium labeling experiments reveal an alkenyl/alkyl mechanism involving allylic internal C(sp2)–H activation and multiple intermolecular 1,2-, 1,3-, and 2,3-hydride shifts. These methods represent new approaches to the functionalization of olefins, and the mechanistic investigations could be helpful for the discovery and design of new strategies for olefin functionalization.

Hypoiodite-catalyzed regioselective oxidation of alkenes: An expeditious access to aldehydes in aqueous micellar media

A highly anti-Markovnikov selective oxidation of alkenes based on in situ generated hypoiodite catalysis in aqueous micellar media under mild conditions has been described. This novel catalytic system realizes an efficient synthesis of aldehydes from alkenes in an economically viable and environmentally safe fashion. The preliminary mechanistic studies suggest that the reaction proceeds via tandem iodofunctionalization/1,2-aryl or alkyl migration. The scope and limitations of this tandem process are demonstrated with various mono- and disubstituted (terminal and internal) olefins.

Phosphate mediated biomimetic synthesis of tetrahydroisoquinoline alkaloids

A one-pot synthesis of tetrahydroisoquinoline alkaloids in a phosphate buffer has been achieved, and a reaction mechanism proposed. The utilisation of mild reaction conditions readily afforded a range of isoquinolines, including norcoclaurine.

Intermediates in the ene reactions of singlet oxygen and N-phenyl-1,2,4-triazoline-3,5-dione with olefins

The reaction between singlet oxygen and cis- and trans-2-butene-1,1,1-d3 has been studied. The product isotope effects (k(H)/k(D)) were found to be 1.38 and 1.25, respectively. Similarly, N-phenyl-1,2,4-triazoline-3,5-dione (PTAD) reacts readily with these substrates and shows isotope effects that are larger (5.36, 1.29) but in the same direction. 2-Methyl-1-propene-3,3,3-d3 is unreactive with singlet oxygen but reacts easily with PTAD with a product isotope effect of 1.25. The intermolecular (kinetic) and intramolecular (product) isotope effects on the reactions of singlet oxygen with cis-1,4-diphenyl-2-butene were found to be 1.07 and 1.50, respectively. cis-Butene is 18 times more reactive with singlet oxygen than the trans isomer. Ene reactions for both singlet oxygen and PTAD probably proceed through the reversible formation of an intermediate with structural requirements similar to a perepoxide or aziridinium imide, respectively.

STEREOSELECTIVE ALDOL CONDENSATIONS OF ORGANOTIN REAGENTS WITH ALDEHYDES

The reaction of the enolstannanes of cyclohexanone or propiophenone with various aldehydes under kinetic control (-78 deg C) gave predominately the threo aldols, diastereoselectivity as high as 95:5 being achived.At higher temperatures (+45 deg C) predominate erythro selectivity was observed.The enolstannane of propiophenone exists as an equilibrium mixture of O-Sn (probably the E-isomer) and C-Sn derivatives.Reaction at -78 deg C takes place rapidly with the O-Sn enolate, further reaction requiring isomerization of the C-Sn to the O-Sn enolate.The Pd catalyzed condensation of cyanomethyltributyltin with reactive aldehydes, such as nitrobenzaldehydes, took place at ambient temperatures in polar solvents to give high yields of condensation products.No reaction occured with aldehydes such as benzaldehyde.Only low stereoselectivity (10-34percent ee) was observed when (-)DIOP or (-)BPPM were utilized as chiral phosphine ligands.