42400-68-0

Upstream product

• 100-42-5 styrene 
• 22979-35-7 Methyl phenyldiazoacetate 
• 536-74-3 phenylacetylene 
• 1073-67-2 4-vinylbenzyl chloride 
• 637-69-4 4-Methoxystyrene 
• 622-97-9 1-ethenyl-4-methylbenzene 
• 402-50-6 1-trifluoromethyl-4-vinyl-benzene 
• 591-50-4 iodobenzene 
• 62360-06-9 rac-(1R,2R)-methyl 1-bromo-2-phenylcyclopropanecarboxylate 
• 67-68-5 dimethyl sulfoxide 
• 101-41-7 benzeneacetic acid methyl ester 
• 128796-39-4 4-trifluoromethylphenylboronic acid 
• 22065-57-2 ethyl 2-phenyldiazoacetate 
• 1078-58-6 diphenylzinc 

Downstream Products

• 42333-01-7 (E)-1,2-diphenylcyclopropanecarboxylic acid 
• 42333-02-8 trans-1,2-diphenyl-1-cyclopropanecarboxylic acid 
• 40164-60-1 methyl 2,4-diphenylbutanoate 
• 55753-44-1 (2,4-Diphenyl-butyl)-dimethyl-amine 
• 10224-13-2 1,2-Diphenyl-cyclopropan-1-carbonsaeure 
• 1413940-37-0 C₂₁H₂₄N₂O 
• 42332-99-0 methyl rel-(1R,2R)-2-ethyl-1,2-diphenylcyclopropanecarboxylate 
• 10223-76-4 (1S,2R)-1,2-Diphenyl-cyclopropanecarboxylic acid amide 
• 10223-76-4 (1S,2S)-1,2-Diphenyl-cyclopropanecarboxylic acid amide 
• 87421-65-6 (-)-(E)-1-cyano-1,2-diphenylcyclopropane 
• 87421-62-3 (+)-(Z)-1-cyano-1,2-diphenylcyclopropane 
• 87395-78-6 (+)-(Z)-1-acetyl-1,2-diphenylcyclopropane 
• 87395-79-7 (+)-(E)-1-acetyl-1,2-diphenylcyclopropane 

Relevant academic research and scientific papers

Well-Defined, Versatile and Recyclable Half-Sandwich Nickelacarborane Catalyst for Selective Carbene-Transfer Reactions

Catalytic carbene-transfer reactions constitute a class of highly useful transformations in organic synthesis. Although catalysts based on a range of transition-metals have been reported, the readily accessible nickel(II)-based complexes have been rarely used. Herein, an air-stable nickel(II)-carborane complex is reported as a well-defined, versatile and recyclable catalyst for selective carbene transfer reactions with low catalyst loading under mild conditions. This catalyst is effective for several types of reactions including diastereoselective cyclopropanation, epoxidation, selective X?H insertions (X = C, N, O, S, Si), particularly for the unprotected substrates. This represents a rare example of carborane ligands in base metal catalysis.

Visible Light-Promoted Sulfoxonium Ylides Synthesis from Aryl Diazoacetates and Sulfoxides

A visible light-promoted reaction of donor/acceptor diazoalkanes with sulfoxides towards the synthesis of synthetically useful sulfoxonium ylides was reported. The reaction occurred under sole visible light irradiation without the need of any transition-metals or additives, affording the corresponding sulfoxonium ylides in moderate to good yields. The success of late-stage modification of natural isolates or drug candidates, scale-up reaction and transformation of sulfoxonium ylides to other useful molecules further rendered the approach valuable.

Blue light-promoted cyclopropenizations of N-tosylhydrazones in water

Carbene transfer reactions play an important role in the field of organic synthesis because of their ability to construct a variety of molecules. Herein, we reported on blue light-induced cyclopropenizations of N-tosylhydrazones in water, which avoids the use of expensive metal-based catalysts and toxic organic solvents. This metal-free and operationally simple methodology enable highly efficient cyclopropenizations, X-H insertion reactions, and cyclopropanation under mild reaction conditions.

Tris(pentafluorophenyl)borane-Catalyzed Cyclopropanation of Styrenes with Aryldiazoacetates

Methods for the synthesis of cyclopropanes are critical for drug discovery, chemical biology, total synthesis, and other fields. Herein, we report the use of the strong sterically encumbered Lewis acid tris(pentafluorophenyl)borane as a catalyst for the cyclopropanation of unactivated alkenes using aryldiazoacetates. The cyclopropane products are synthesized using 10 mol % of the catalyst under mild conditions in up to 90% yield (8:1 to >20:1 dr). We propose that the reaction proceeds via a Lewis acid-activated carbene.

Room Temperature Coupling of Aryldiazoacetates with Boronic Acids Enhanced by Blue Light Irradiation

A visible-light-promoted photochemical protocol is reported for the coupling of aryldiazoacetates with boronic acids. This photochemical reaction shows great enhancement compared to the same protocol performed in the absence of light. Except for a few cases, the room temperature coupling in the dark (thermal process) generally does not work. When it does, it is likely to also involve free carbenes as key intermediates. Alternatively, photochemical reactions show a broad scope, can be performed under air and tolerate a wide variety of functional groups. Reaction-evolution monitoring, DFT calculations and control experiments have been used to evaluate the main aspects of this intricate mechanistic scenario. Biologically active molecules Adiphenine, Benactyzine and Aprophen have been prepared as examples of synthetic applications.

Blue Light-promoted Carbene Transfer Reactions of Tosylhydrazones

Metal-free photochemical carbene-transfer reactions of tosylhydrazones were developed under blue light irradiation at room temperature. This reaction constructs C?X (X=C, N, O, S) bonds and cyclopropanes from readily available and stable starting material

Blue light-promoted N–H insertion of amides, isatins, sulfonamides and imides into aryldiazoacetates: Synthesis of unnatural α-aryl amino acid derivatives

A photochemical protocol using blue light allows the N–H insertion of amides, isatins, sulfonamides and imides into aryldiazoacetates to afford the corresponding α-amino esters. This method is experimentally simple, inexpensive and tolerates numerous functional groups, thus allowing the straightforward preparation of a variety of α-aryl amino acid derivatives in good yields.

Bis(imino)pyridine iron complexes for catalytic carbene transfer reactions

The bis(imino)pyridine iron complex, for the first time, is developed as an effective metal carbene catalyst for carbene transfer reactions of donor-acceptor diazo compounds. Its broad catalytic capability is demonstrated by a range of metal carbene reactions, from cyclopropanation, cyclopropenation, epoxidation, and Doyle-Kirmse reaction to O-H insertion, N-H insertion, and C-H insertion reactions. The asymmetric cyclopropanation of styrene and methyl phenyldiazoacetate was successfully achieved by the new chiral bis(imino)pyridine iron catalyst, which delivers a new gateway for the development of chiral iron catalysis for metal carbene reactions.

Synthesis of Chiral Bifunctional NHC Ligands and Survey of Their Utilities in Asymmetric Gold Catalysis

The synthesis and characterization of the chiral bifunctional NHC ligands based on the imidazo[1,5-a]pyridine (ImPy) scaffold are described. These ligands possess a fluxional biaryl axis and a chiral center. The configurational stability of the biaryl axis in their gold(I) complexes is investigated. The application of these axially chiral ImPy-based AuCl complexes in a series of gold catalysis is explored, and varying degrees of asymmetric induction are observed. In most cases, the ligand (aS,R)-L8-H with its cyclohexyl group pointing to the reaction site and hence exerting asymmetric steric influence is more effective in asymmetric induction.

Isolation of a Reactive Tricoordinate α-Oxo Gold Carbene Complex

The [(P,P)Au=C(Ph)CO2Et]+ complex 3 [where (P,P) is an o-carboranyl diphosphine ligand] was prepared by diazo decomposition at ?40 °C. It is the first α-oxo gold carbene complex to be characterized. Its crystallographic structure was determined and DFT calculations have been performed, unraveling the key influence of the chelating (P,P) ligand. The gold center is tricoordinate and the electrophilicity of the carbene center is decreased. Complex 3 mimics transient α-oxo gold carbenes in a series of catalytic transformations, and provides support for the critical role of electrophilicity in the chemoselectivity of phenol functionalization (O?H vs. C?H insertion).