102002-24-4

Upstream product

• 29180-91-4 1-phenyl-4-(1-phenylvinyl)cyclohex-1-ene 
• 98-80-6 phenylboronic acid 
• 320369-29-7 N′-(1-([1,1′-biphenyl]-4-yl)ethylidene)-4-methylbenzenesulfonohydrazide 
• 92-91-1 biphenyl-4-acetaldehyde 
• 585-71-7 (1-bromoethyl)benzne 
• 144432-80-4 2-(biphenyl-4-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane 
• 7598-80-3 4-phenylbenzhydrol 
• 75-24-1 trimethylaluminum 
• 75230-51-2 4-bromoacetophenone tosylhydrazone 
• 99-90-1 para-bromoacetophenone 
• 40231-42-3 4-(1-phenylvinyl)-1,1′-biphenyl 
• 100-42-5 styrene 
• 92-66-0 4-bromo-1,1'-biphenyl 
• 3315-91-1 4-biphenylylmagnesium bromide 

Relevant academic research and scientific papers

Reductive cross-coupling of conjugated arylalkenes and aryl bromides with hydrosilanes by cooperative palladium/copper catalysis

A method for the reductive cross-coupling of conjugated arylalkenes and aryl bromides with hydrosilanes by cooperative palladium/copper catalysis was developed, thus resulting in the highly regioselective formation of various 1,1-diarylalkanes, including a biologically active molecule. Under the applied reaction conditions, high levels of functional-group tolerance were observed, and the reductive cross-coupling of internal alkynes with aryl bromides afforded trisubstituted alkenes. Forming a Co-op: A method for the reductive cross-coupling of conjugated arylalkenes or internal alkynes and aryl bromides with hydrosilanes using cooperative palladium/copper catalysis was developed. The resulting 1,1-diarylalkanes and trisubstituted alkenes were isolated with high regio- and stereoselectivity. Under the applied reaction conditions, high levels of functional-group tolerance were observed.

A general copper-catalyzed radical C(sp3)?C(sp2) cross-coupling to access 1,1-diarylalkanes under ambient conditions

A general copper-catalyzed C(sp3)?C(sp2) cross-coupling of (hetero)benzyl bromides with the air- and moisture-stable aryl nucleophiles has been developed, providing a facile access to pharmaceutically useful 1,1-di(hetero)arylalkane and 1-aryl-1-heteroarylalkane scaffolds. Critical to the success is the utilization of a proline-based N,N,P-ligand to enhance the reducing capability of copper, thus easily converting benzyl bromides to the corresponding radical species via a single-electron transfer process under ambient conditions. The reaction features a broad substrate scope, covering (hetero)arylboronate esters, oxadiazoles, and benzo[d]oxazoles, as well as primary and secondary (hetero)benzyl bromides with excellent functional group tolerance.

Copper-Catalyzed Enantioconvergent Radical Suzuki-Miyaura C(sp3)-C(sp2) Cross-Coupling

A copper-catalyzed enantioconvergent Suzuki-Miyaura C(sp3)-C(sp2) cross-coupling of various racemic alkyl halides with organoboronate esters has been established in high enantioselectivity. Critical to the success is the use of a chiral cinchona alkaloid-derived N,N,P-ligand for not only enhancing the reducing capability of copper catalyst to favor a stereoablative radical pathway over a stereospecific SN2-type process but also providing an ideal chiral environment to achieve the challenging enantiocontrol over the highly reactive radical species. The reaction has a broad scope with respect to both coupling partners, covering aryl- and heteroarylboronate esters, as well as benzyl-, heterobenzyl-, and propargyl bromides and chlorides with good functional group compatibility. Thus, it provides expedient access toward a range of useful enantioenriched skeletons featuring chiral tertiary benzylic stereocenters.

Synthesis of 1,1′-diarylethanes and related systems by displacement of trichloroacetimidates with trimethylaluminum

Benzylic trichloroacetimidates are readily displaced by trimethylaluminum under Lewis acid promoted conditions to provide the corresponding methyl substitution product. This method is a convenient way to access 1,1′-diarylethanes and related systems, which play a significant role in medicinal chemistry, with a number of systems owing their biological activity to this functionality. Most benzylic substrates undergo ready displacement, with electron deficient systems being the exception. The use of an enantiopure imidate showed significant racemization, implicating the formation of a cationic intermediate.

One-pot reductive coupling reactions of acetyl naphthalene derivatives, tosylhydrazide, with arylboronic acids

In this study, a one-pot two-step reductive coupling between acetyl naphthalene derivatives, tosylhydrazide, and arylboronic acids, affording substituted 1(or 2)-(1-phenylethyl)naphthalenes in moderate-to-excellent yields, was reported. Notably, solvent played a crucial role in the coupling of 1-acetyl naphthalene derivatives (toluene) or 2-acetyl naphthalene derivatives (1,4-dioxane) as starting materials. Meanwhile, the scope of this one-pot coupling reaction was extended to 1(or 2)-naphthaldehyde substrates. Particularly, the system was also suitable to synthesize 1(or 2)-(1-phenylethyl)naphthalenes on a multi-gram scale, and was applied in the synthesis of naphthylmethyl substituted carbazolyl compounds.

Multi-component one-pot reaction of aromatic carbonyl compounds, tosylhydrazide, and arylboronic acids

In this paper, we developed a new method using 4-bromoacetophenone as the starting material, with tosylhydrazide and two arylboronic acids using Barluenga and Suzuki couplings in a four-component one-pot reaction to afford the target product 4-benzyl-1,1-biphenyls. This system that we have developed enables the use of easily accessible starting materials and can be employed on a wide variety of substrates with good functional group tolerance. In particular, this protocol can be applied to the synthesis of 4-(1-([1,1-biphenyl]-4-yl)ethyl)pyridine derivatives, a class of potential analogs of CPY17 inhibitors of prostate cancer.

Traceless directing group mediated branched selective alkenylation of unbiased arenes

Owing to the synthetic importance of branched olefinated products, we report palladium catalyzed formation of branched olefins facilitated by a C-H activation based protocol. This involves selective insertion of olefins and subsequent decarboxylation using a completely unbiased benzene ring as the starting precursor. The significance of the protocol has been further highlighted by exhibition of functionality tolerance along with a late-stage modification of the branched olefinated products leading to the formation of other functionalized molecules.

Palladium-catalyzed cross-coupling reaction of secondary benzylic bromides with grignard reagents

"Chemical Equation Presented" A mild palladium-catalyzed Kumada-Corriu reaction of secondary benzylic bromides with aryl and alkenyl Grignard reagents has been developed. In the presence of the Xantphos ligand, the undesired β-elimination pathway Is minimized, affording the corresponding cross-coupling products In acceptable to good yields. The reaction proceeds with inversion of the configuration.