1190259-69-8

Upstream product

• 591-17-3 meta-bromotoluene 
• 98-83-9 isopropenylbenzene 
• 29526-96-3 1-phenylcyclopropan-1-ol 
• 4382-80-3 1-phenylcyclopropyl 4-methylbenzenesulfonate 
• 17933-03-8 m-tolylboronic acid 
• 98-81-7 1-bromovinylbenzene 
• 625-95-6 3-Iodotoluene 
• 77130-15-5 2-phenylallyltrimethylsilane 
• 3333-20-8 1-allyl-3-methylbenzene 
• 100-58-3 phenylmagnesium bromide 

Relevant academic research and scientific papers

Boronic acid-mediated ring-opening and Ni-catalyzed arylation of 1-arylcyclopropyl tosylates

Herein, we describe a protocol for the ring-opening arylation of 1-arylcyclopropyl tosylates, in which boronic acids promote ring-opening and a Ni catalyst facilitates arylation in high regioselectivity. A number of 2-arylated allyl derivatives are synthesized, which are relevant motifs found in biologically active molecules.

Silver-promoted cross-coupling of substituted allyl(trimethyl)silanes with aryl iodides by palladium catalysis

A ligand-free Pd-catalyzed cross-coupling of substituted allyl(trimethyl)silanes with aryl iodides enabled by silver salts was developed. This reaction delivered allylic arenes chemoselectively and regioselectively. The study suggested that the reaction might proceed through oxidative addition of ArI to Pd(0) followed by halide abstraction to give an electrophilic complex ArPdX, which further reacted with allyl(trimethyl)silanes via electrophilic addition/desilylation/reductive elimination to afford the allyl-aryl coupling products.

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.

Preparation method of 1, 1-disubstituted olefin

The invention provides a preparation method of 1, 1-disubstituted olefin. The preparation method includes the steps of A), under the catalysis of a metallic nickel compound, allowing a compound as shown in formula (II) to have reaction with Grignard reagent as shown in formula (III) under protective atmosphere to obtain the 1, 1-disubstituted olefin as shown in formula (I), wherein R1 is alkyl, substituted alkyl, aryl or substituted aryl, and R2 is aryl or substituted aryl. Compared with the prior art, the preparation method has the advantages that the method is simple in raw material, wide in raw material source, mild in reaction condition and high in selectivity, only the 1, 1-disubstituted olefin is prepared, and the isomer of the 1, 1-disubstituted olefin does not exist.

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.

1,1′-methylene-3,3′-bis[(N -(tert -butyl)imidazol-2-ylidene] and Its effect in palladium-catalyzed C-C coupling

A catalytic system utilizing a chelate carbene ligand containing bulk tert-butyl groups is described for palladium-catalyzed Heck and Suzuki coupling reactions. The Heck reaction focused on the coupling of different aryl bromides with mono- and 1,1-disubstituted olefins while the Suzuki reaction involved the coupling of aryl bromides and phenylboronic acid to afford the corresponding biphenyls. The catalyst system performs well with low Pd(OAc)2 levels (0.025 mol% Pd). In all cases with monosubstituted olefins, the trans-configured products were obtained, while the results of Heck reaction of 1,1-disubstituted olefins exhibited a high selectivity favoring the terminal product.

Selective arylation of 1,1-disubstituted olefins using a biphenyl-based phosphine in Heck coupling reactions

The biphenyl-based phosphine, 2-diphenylphosphino-2′-methylbiphenyl is an effective ligand for palladium-catalyzed terminal arylation of 1,1-disubstituted olefins with aryl bromides in DMF and K2CO3 as base. The yields of products are independent of the electronic properties of the aryl bromides, however, the nature of the olefin has a major effect.