7555-67-1

Upstream product

• 3607-17-8 3-bromopropyltriphenylphosphonium bromide 
• 100-52-7 benzaldehyde 
• 186581-53-3 diazomethane 
• 2327-99-3 1-phenylpropadiene 
• 14633-95-5 triphenylphosphonium cyclopropylide 
• 74592-24-8 Cyclopropanone Ethyl Hemiketal Magnesium Iodide 
• 29817-09-2 1-methylene-2-phenylcyclopropane 
• 115413-56-4 [1-(Diphenyl-phosphinoyl)-cyclopropyl]-phenyl-methanol 
• 14114-05-7 cyclopropyltriphenylphosphonium bromide 
• 16721-45-2 triphenyl(phenylmethylene)phosphorane 
• 51417-12-0 ((cyclopropylsulfonyl)methyl)benzene 
• 688358-89-6 pentachlorophenyl cyclopropyl sulfone 
• 7333-63-3 4-bromobutylphosphonium bromide 

Downstream Products

• 56152-81-9 1,1-Dichlor-2-phenylspiro<2.2>pentan 
• 37862-48-9 2-Butyl-1-phenylcyclobuten 
• 41893-70-3 1-(1-bromo-1-phenylmethyl)cyclopropyl bromide 
• 56061-49-5 1-[1-(Chloro-phenyl-methyl)-cyclopropylsulfanyl]-2,4-dinitro-benzene 
• 56061-51-9 1-{3-Chloro-1-[1-phenyl-meth-(Z)-ylidene]-propylsulfanyl}-2,4-dinitro-benzene 
• 56061-50-8 Acetic acid [1-(2,4-dinitro-phenylsulfanyl)-cyclopropyl]-phenyl-methyl ester 
• 115073-17-1 Hexahydro-6',6'-dimethyl-2-phenyl-spiroisoxazole> 
• 115073-13-7 Hexahydro-6',6'-dimethyl-3-phenylspiroisoxazole> 
• 113327-83-6 6-Methyl-7-phenyl-4-oxa-5-azaspiro<2.4>hept-5-ene 
• 113327-84-7 4-Methyl-7-phenyl-6-oxa-5-azaspiro<2.4>hept-4-ene 
• 120587-84-0 4-[1-Phenyl-meth-(E)-ylidene]-hexahydro-pentalen-1-one 
• 1005-64-7 trans-1-phenyl-1-butene 
• 29817-09-2 1-methylene-2-phenylcyclopropane 
• 7302-03-6 (E)-2-methyl-1-phenyl-1-butene 

Relevant academic research and scientific papers

Oxidative Ring Expansion of Cyclobutanols: Access to Functionalized 1,2-Dioxanes

Cyclobutanols undergo an oxidative ring expansion with Co(acac)2 and triplet oxygen to give 1,2-dioxanols. The formation of an alkoxy radical drives the regioselective cleavage of the ring on the more substituted side before insertion of molecular oxygen. The reaction is particularly effective on secondary cyclobutanols but works also on certain tertiary alcohols. Further substitution with neutral nucleophiles under catalytic Lewis acid conditions led to original 1,2-dioxanes with a preferred 3,6-cis-configuration.

Iron-Catalyzed Regioselective Alkenylboration of Olefins

The first examples of an iron-catalyzed three-component synthesis of homoallylic boronates from regioselective union of bis(pinacolato)diboron, an alkenyl halide (bromide, chloride or fluoride), and an olefin are disclosed. Products that bear tertiary or quaternary carbon centers could be generated in up to 87 % yield as single regioisomers with complete retention of the olefin stereochemistry. With cyclopropylidene-containing substrates, ring cleavage leading to trisubstituted E-alkenylboronates were selectively obtained. Mechanistic studies revealed reaction attributes that are distinct from previously reported alkene carboboration pathways.

Gem-Difluorination of Methylenecyclopropanes (MCPs) Featuring a Wagner-Meerwein Rearrangement: Synthesis of 2-Arylsubstituted gem-Difluorocyclobutanes

The geminal difluorocyclobutane core is a valuable structural element in medicinal chemistry. Strategies for gem-difluorocyclobutanes, especially the 2-substituted cases, are limiting and often suffer from harsh reaction conditions. Reported herein is a m

Copper-Catalyzed Enantioselective Arylation via Radical-Mediated C-C Bond Cleavage: Synthesis of Chiral ω,ω-Diaryl Alkyl Nitriles

The first example of copper-catalyzed ring-opening, enantioselective arylation of cyclic ketoxime esters to access ω,ω-diaryl alkyl nitriles has been developed in high yield (up to 92% yield) with excellent enantioselectivity (up to 91% ee). Side-arm bis(oxazoline) ligand plays a significant role in this asymmetric catalytic transformation, which provides an efficient route to construct diverse chiral ω,ω-diaryl alkyl nitriles. Synthetic utility has also been demonstrated in the further derivatization of the ω,ω-diaryl alkyl nitrile to the corresponding amide.

Visible-Light Photoredox-Catalyzed Dicarbofunctionalization of Styrenes with Oxime Esters and CO2: Multicomponent Reactions toward Cyanocarboxylic Acids and γ-Keto Acids

A photoredox-catalyzed dicarbofunctionalization of styrenes with oxime esters and CO2 has been achieved. Notably, a series of four-, five-, or six-membered cyclic ketone oximes worked well to furnish a wide range of ε-, ζ-, and η-cyanocarboxylic acids in good yields. Furthermore, a series of γ-keto acids also could be obtained by employing acyclic ketone oxime esters as the carbonyl radical precursor. It provides convergent access to diverse biologically important cyanocarboxylic and γ-keto acids.

Nickel-Catalyzed Favorskii-Type Rearrangement of Cyclobutanone Oxime Esters to Cyclopropanecarbonitriles

A nickel-catalyzed base-promoted rearrangement of cyclobutanone oxime esters to cyclopropanecarbonitriles was developed. The ring opening of cyclobutanone oxime esters occurs at the sterically less hindered side. A base-promoted nickelacyclobutane intermediate, formed in situ, is assumed to be involved in the formation of the product.

Cobalt(iii)-catalyzed redox-neutral [4+2]-annulation ofN-chlorobenzamides/acrylamides with alkylidenecyclopropanes at room temperature

An efficient synthesis of substituted 3,4-dihydroisoquinolinones through [4+2]-annulation ofN-chlorobenzamides/acrylamides having a monodentate directing group with alkylidenecyclopropanes in the presence of a less expensive, highly abundant and air stable Co(iii) catalystviaa C-H activation is demonstrated. In this reaction, the N-Cl bond ofN-chlorobenzamide serves as an internal oxidant and thus an external metal oxidant is avoided. The 3,4-dihydroisoquinolinone derivatives are converted successfully into the highly useful imidoyl chloride derivatives. The deuterium labeling and kinetic isolabelling studies reveal that the C-H activation is a rate-determining step in this cyclization reaction.

Activation and Functionalization of C-C σ Bonds of Alkylidene Cyclopropanes at Main Group Centers

Aluminum(I) and magnesium(I) compounds are reported for the C-C σ-bond activation of strained alkylidene cyclopropanes. These reactions result in the formal addition of the C-C σ bond to the main group center either at a single site (Al) or across a metal-metal bond (Mg-Mg). Mechanistic studies suggest that rather than occurring by a concerted oxidative addition, these reactions involve stepwise processes in which substrate binding to the main group metal acts as a precursor to α- or β-alkyl migration steps that break the C-C σ bond. This mechanistic understanding is used to develop the magnesium-catalyzed hydrosilylation of the C-C σ bonds of alkylidene cyclopropanes.

Ring opening of methylenecyclopropanes with halides in liquid sulfur dioxide

Methylenecyclopropanes (MCP) undergo ring opening reactions with group I and II metal halides and ammonium halides in liquid SO2 to afford homoallylic halides, which are versatile reagents in organic synthesis. The developed reaction conditions are compatible with acid-labile substrates such as N-Boc-protected compounds. Liquid SO2 is a polar reaction medium with Lewis acid properties that solubilizes inorganic salts. The unique properties of SO2 were demonstrated by control experiments: 1) upon performing the reactions with the aforementioned salts in conventional solvents, the MCP ring opening was not observed either in the presence of catalytic amounts of H3PO4 (similar pKa to that of H2SO3), or in the absence of H3PO4; 2) a solution of SO2 in THF exhibited similar properties to that of liquid SO2.

Radical-Cation Vinylcyclopropane Rearrangements by TiO2Photocatalysis

Radical cation vinylcyclopropane rearrangements by TiO2 photocatalysis in lithium perchlorate/nitromethane solution are described. The reactions are triggered by oxidative single electron transfer, which is followed by immediate ring-opening of the cyclopropanes to generate distonic radical cations as unique reactive intermediates. This approach can also be applied to vinylcyclobutane, leading to the construction of six-membered rings. A stepwise mechanism via distonic radical cations is proposed based on preliminary mechanistic studies, which is supported by density functional theory calculations.