102549-93-9

Upstream product

• 2038-57-5 3-Phenylpropan-1-amine 
• 4760-34-3 N-methyl-1,2-phenylenediamine 
• 100-42-5 styrene 
• 1632-83-3 1-Methylbenzimidazole 

Downstream Products

• 108641-77-6 2-(1-methyl-1H-benzo[d]imidazol-2-yl)-1-phenylethan-1-ol 

Relevant academic research and scientific papers

A dual biomimetic process for the selective aerobic oxidative coupling of primary amines using pyrogallol as a precatalyst. Isolation of the [5 + 2] cycloaddition redox intermediates

A bioinspired organocatalytic cascade reaction mimicking both purpurogallin biosynthesis and copper amine oxidases (CuAOs) activity is described, at room temperature under ambient air, for the activation of the α-C-H bond of primary amines. The reaction sequence uses low-cost commercially available pyrogallol as a precatalyst which undergoes an in situ oxidative self-processing step, resulting in its conversion into natural purpurogallin, a [5 + 2] cycloaddition redox intermediate. This is further involved in the CuAOs-like transamination mechanism for producing, under single turnover, the active biomimetic organocatalyst which mediates the selective oxidative coupling of primary amines, including the non-activated substrates of CuAOs. Without any metal cocatalyst or additives, the protocol gives access to cross-coupled imines as well as 1,2-disubstituted benzimidazoles. The isolation of not easily accessible [5 + 2] cycloaddition redox intermediates provides direct and clear evidence for the proposed dual biomimetic process.

N-Heterocyclic Carbene Ligand-Controlled Regioselectivity for Nickel-Catalyzed Hydroarylation of Vinylarenes with Benzothiazoles

A facile regioselective switch for nickel-catalyzed hydroarylation of vinylarenes with benzothiazoles has been developed, which relies on the simple structural variation of novel Ni(II) complexes of the type Ni(NHC)[P(OR)3]Br2. Using magnesium turnings as the reductant, Ni(IMes)[P(OEt)3]Br2 afforded branched products, while Ni(IPr?OMe)[P(OEt)3]Br2 created steric demand to afford linear products. This work also provides a rare example of the rational design of heteroleptic Ni(II) complexes that display the required air stability, reactivity, and regioselectivity via synergism between NHC and phosphite ligands.

Method for synthesizing 1,2-bibenzyl compound

The invention discloses a method for synthesizing a 1,2-bibenzyl compound. According to the method, a nickelous (II) complex with the molecular formula being Ni[P(OEt)3][(RNCHCHNR)C]Br2 serves as a catalyst, wherein R is 2,6-diphenyl methyl-4-methoxyphenyl), and in the presence of metal magnesium, the 1,2-bibenzyl compound is synthesized through a cross-coupling reaction of benzo-(hetero)arene anda styrene compound. According to the method, the nickelous (II) complex with air stability serves as the catalyst for the first time, so that direct use of sensitive and dangerous metal compounds andzero-valent nickel (0) complexes is avoided; under mild reaction conditions, a zero-valent nickel (0) active center is formed in situ through the action of the metal magnesium, so that the cross-coupling reaction between the benzo-(hetero)arene and the styrene compound is achieved, and a novel method is provide for synthesis of the 1,2-bibenzyl compound.

A Bioinspired Organocatalytic Cascade for the Selective Oxidation of Amines under Air

A bioinspired organocatalytic cascade reaction for the selective aerobic oxidative cross-coupling of primary amines to imines is described. This approach takes advantages of commercially available pyrogallol monomeric precursor to deliver low loadings of natural purpurogallin in situ, under air. This is further engaged in a catalytic process with the amine substrate affording, under single turnover, the active biomimetic quinonoid organocatalyst and the homocoupled imine intermediate, which is then converted into cross-coupled imine after dynamic transimination. This organocatalytic cascade inspired by both purpurogallin biosynthesis and copper amine oxidases allows the aerobic oxidation of non-activated primary amines that non-enzymatic organocatalysts were not able to accomplish alone.

Mechanistic study of a switch in the regioselectivity of hydroheteroarylation of styrene catalyzed by bimetallic Ni-Al through C-H activation

We previously reported a highly efficient protocol for bimetallic Ni-Al-catalyzed hydroheteroarylation of styrene with benzimidazole based on C-H bond activation. We have now delineated the mechanism of this process, providing a rationale for an observed switch in regioselectivity in the presence of the Lewis acid, AlMe3. The present mechanistic study gives insights for the rational development of catalysts that exhibit required linear/branched selectivity. Lewis acid switches regioselectivity: The mechanism underpinning a highly efficient protocol for bimetallic Ni-Al-catalyzed hydroheteroarylation of styrene with benzimidazole based on C-H bond activation has been unraveled (see scheme). The study gives insights that can be used for the rational development of catalysts that give the required linear/branched selectivity.

The regioselective switch for amino-NHC mediated C-H activation of benzimidazole via Ni-Al synergistic catalysis

We have disclosed a new mode of a chemically regioselective switch for C-H bond functionalization of benzimidazole derivatives via a cooperative effect invoked by Ni-Al bimetallic catalysis to create a steric requirement for obtaining the linear product of styrene insertion. Yet, excluding the AlMe 3 cocatalyst switches the reaction toward branch selectivity.