22979-36-8

Upstream product

• 23786-14-3 4-methoxy-phenyl acetic acid methyl ester 
• 32766-61-3 4-methoxyphenylglyoxylate methyl ester 
• 104-01-8 4-Methoxyphenylacetic acid 
• 22979-34-6 Methyl-p-methoxyphenylglyoxylat-hydrazon 

Relevant academic research and scientific papers

Synthesis of Functionalized Silsesquioxane Nanomaterials by Rhodium-Catalyzed Carbene Insertion into Si?H Bonds

We report carbene insertion into Si?H bonds of polyhedral oligomeric silsesquioxanes (POSS) for the synthesis of highly functionalized siloxane nanomaterials. Dirhodium(II) carboxylates catalyze insertion of aryl-diazoacetates as carbene precursors to afford POSS structures containing both ester and aryl groups as orthogonal functional handles for further derivatization of POSS materials. Four diverse and structurally varied silsesquioxane core scaffolds with one, three, or eight Si?H bonds were evaluated with diazo reactants to produce a total of 20 new POSS compounds. Novel diazo compounds containing a fluorinated octyl group and boron-dipyrromethene (BODIPY) chromophore demonstrate the use of highly functionalized substrates. Transformations of aryl(ester)-functionalized POSS compounds derived from this method are demonstrated, including ester hydrolysis and Suzuki–Miyaura cross-coupling.

Borane catalysed cyclopropenation of arylacetylenes

Triarylboranes have gained substantial attention as catalysts for C-C bond forming reactions due to their remarkable catalytic activities. Herein, we report B(C6F5)3catalysed cyclopropenation of a wide variety of arylacetylenes using donor-acceptor diazoesters. A mild reaction protocol has been developed for the synthesis of functionalised cyclopropenes (33 examples) in good to excellent yields.

Catalyst-free, scalable heterocyclic flow photocyclopropanation

Industrial process development is driven by several factors, including safety, cost, robustness and environmental aspects. However, attempts to establish aryl diazo esters-which are highly valued in academic research for their reactivity as carbene precur

Borane Catalyzed Selective Diazo Cross-Coupling Towards Pyrazoles

Decomposition of donor-acceptor diazo compounds leads to the formation of reactive carbene intermediates. These can undergo a wide variety of carbene transfer reactions to yield synthetically useful products. Herein, we report a selective borane catalyzed cyclization reaction from the combination of two different diazo compounds to afford N-substituted pyrazoles. The selective decomposition of the more reactive α-aryl α-diazoester and subsequent reaction with a vinyl diazoacetate produces N-alkylated pyrazoles in a regioselective manner. Catalytic amounts of tris(pentafluorophenyl)borane (10 mol%) were employed to afford the pyrazole products (36 examples) in yields from 59 to 80%. Extensive DFT studies have been undertaken to interpret the mechanism for this reaction which was found to go through two tandem catalytic cycles, both catalyzed by B(C6F5)3.

Azide Radical Initiated Ring Opening of Cyclopropenes Leading to Alkenyl Nitriles and Polycyclic Aromatic Compounds

We report herein a radical-mediated amination of cyclopropenes. The transformation proceeds through a cleavage of the three-membered ring after the addition of an azide radical on the strained double bond and leads to tetrasubstituted alkenyl nitrile derivatives upon loss of N2. With 1,2-diaryl substituted cyclopropenes, this methodology could be extended to a one-pot synthesis of highly functionalized polycyclic aromatic compounds (PACs). This transformation allows the synthesis of nitrile-substituted alkenes and aromatic compounds from rapidly accessed cyclopropenes using only commercially available reagents.

Engineering Dirhodium Artificial Metalloenzymes for Diazo Coupling Cascade Reactions**

Artificial metalloenzymes (ArMs) are commonly used to control the stereoselectivity of catalytic reactions, but controlling chemoselectivity remains challenging. In this study, we engineer a dirhodium ArM to catalyze diazo cross-coupling to form an alkene that, in a one-pot cascade reaction, is reduced to an alkane with high enantioselectivity (typically >99 % ee) by an alkene reductase. The numerous protein and small molecule components required for the cascade reaction had minimal effect on ArM catalysis. Directed evolution of the ArM led to improved yields and E/Z selectivities for a variety of substrates, which translated to cascade reaction yields. MD simulations of ArM variants were used to understand the structural role of the cofactor on ArM conformational dynamics. These results highlight the ability of ArMs to control both catalyst stereoselectivity and chemoselectivity to enable reactions in complex media that would otherwise lead to undesired side reactions.

Dirhodium(II)/Xantphos-Catalyzed Relay Carbene Insertion and Allylic Alkylation Process: Reaction Development and Mechanistic Insights

Although dirhodium-catalyzed multicomponent reactions of diazo compounds, nucleophiles and electrophiles have achieved great advance in organic synthesis, the introduction of allylic moiety as the third component via allylic metal intermediate remains a formidable challenge in this area. Herein, an attractive three-component reaction of readily accessible amines, diazo compounds, and allylic compounds enabled by a novel dirhodium(II)/Xantphos catalysis is disclosed, affording various architecturally complex and functionally diverse α-quaternary α-amino acid derivatives in good yields with high atom and step economy. Mechanistic studies indicate that the transformation is achieved through a relay dirhodium(II)-catalyzed carbene insertion and allylic alkylation process, in which the catalytic properties of dirhodium are effectively modified by the coordination with Xantphos, leading to good activity in the catalytic allylic alkylation process.

B(C6F5)3-catalyzed O-H insertion reactions of diazoalkanes with phosphinic acids

A highly efficient base-, metal-, and oxidant-free catalytic O-H insertion reaction of diazoalkanes and phosphinic acids in the presence of B(C6F5)3has been developed. This powerful methodology provides a green approach towards the synthesis of a broad spectrum of α-phosphoryloxy carbonyl compounds with good to excellent yields (up to 99% yield). The protocol features the advantages of operational simplicity, high atom economy, practicality, easy scalability and environmental friendliness.

Divergent Synthesis of Aziridine and Imidazolidine Frameworks under Blue LED Irradiation

We develop a visible light-promoted divergent cycloaddition of α-diazo esters with hexahydro-1,3,5-triazines, leading to a series of aziridine and imidazolidine frameworks in average good yield, by simply changing the reaction media used. It is noteworthy that the reaction occurs under sole visible light irradiation without the need for exogenous photoredox catalysts. More significantly, a reasonable reaction mechanism was proposed on the basis of the control experiments and density functional theory calculation results.

Visible-Light-Promoted Polysubstituted Olefins Synthesis Involving Sulfur Ylides as Carbene Trapping Reagents

A blue-light-emitting diode (LED) promoted coupling of aryl diazoacetates with sulfur ylides is described. This protocol features mild conditions, good functional group tolerance, and broad substrate scope for both aryl diazoacetates with sulfur ylides. Under optimal reaction conditions, a wide range of trisubstituted olefins is obtained in moderate to good yield, which can be further transferred to other biologically important heterocycles after a two-step simple operation.