91176-32-8

Upstream product

• 88106-19-8 C₁₆H₁₇NO₃S₂ 
• 1195-32-0 1-methyl-4-isopropenylbenzene 
• 591-87-7 Allyl acetate 
• 624-31-7 4-tolyl iodide 
• 98-80-6 phenylboronic acid 
• 1415643-25-2 1-methyl-4-(2-tolyl-prop-2-ene-1-sulfonyl)-benzene 
• 58109-40-3 diphenyliodonium hexafluorophosphate 
• 300-57-2 allylbenzene 
• 4294-57-9 para-methylphenylmagnesium bromide 
• 139214-35-0 trimethyl(2-(4-methylphenyl)allyl)silane 
• 108-88-3 toluene 
• 1779-49-3 Methyltriphenylphosphonium bromide 
• 2001-28-7 2-phenyl-1-p-tolyl-ethanone 

Downstream Products

• 58662-08-1 (E)-1-methyl-4-(1-phenylprop-1-en-2-yl)benzene 
• 61820-95-9 2-(toluene-4-sulfonyl)-1-p-tolylethanone 

Relevant academic research and scientific papers

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.

Oxidative cross-coupling of allyl(trimethyl)silanes with aryl boronic acids by palladium catalysis

The first oxidative cross-coupling of allylsilanes with aryl boronic acids has been developed by palladium catalysis. The reaction between β-substituted allyl(trimethyl)silanes and a wide range of aryl boronic acids afforded allylarenes in moderate to good yields and excellent selectivity. On the basis of experimental results and literature reports, it was suggested that the reaction might start from transmetalation of aryl boronic acid with AgOAc followed by transmetalation with Pd(II) to give an arylpalladium acetate complex as a key intermediate. This intermediate underwent either electrophilic addition/desilylation or transmetalation with allylsilane and subsequent reductive elimination to give the final product.

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.

Aryl radical formation by copper(I) photocatalyzed reduction of diaryliodonium salts: NMR Evidence for a CuII/CuI mechanism

Photocatalyzed reduction of diaryliodonium salts was achieved by using [Cu(dpp)2][PF6] as a photoactive complex and DIPEA as a reductive quench. The application of a copper catalyst allows the generation of aryl radicals under mild conditions and maintains their reactivity for C-C bond formation processes.

Synthesis of 1,3-diarylpropenes through palladium-catalyzed mizoroki-heck and allyl cross-coupling reactions using hydrazones as ligands

The palladium-catalyzed synthesis of unsymmetrical 1,3-diarylpropenes from allyl esters through a Mizoroki-Heck-type reaction with aryl iodides followed by allyl cross-coupling with a variety of arylboronic acids was developed; the products are obtained in moderate to good yields by using a hydrazone-Pd(OAc) 2 system. The synthesis of unsymmetrical 1,3-diarylpropenes from allyl esters by a Mizoroki-Heck-type reaction followed by allyl cross-coupling with a variety of arylboronic acids was developed; the products were obtained in moderate to good yields by using a hydrazone-Pd(OAc)2 system. Copyright

ALKYLATION DE TERPENES EN DEUX ETAPES PAR ENE-REACTION

A simple, two-step homologation of terpenes is reported that requires ene-reaction with PhSO2NSO and subsequent of the intermediate adducts with CuI catalyzed Grignard