34672-84-9

Upstream product

• 7031-93-8 2,2,6,6-tetramethylpiperidin-1-ol 
• 74-88-4 methyl iodide 
• 2564-83-2 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical 
• 515176-03-1 [Pd(2-diphenylphosphino-4-methylphenol)(CH3)(μ-Cl)]2 
• 146801-38-9 (E)-4,4,4-trifluoro-1,3-diphenyl-2-buten-1-one 
• 75-91-2 tert.-butylhydroperoxide 
• 123-11-5 4-methoxy-benzaldehyde 
• 110-05-4 di-tert-butyl peroxide 
• 25982-72-3 2-methyl-3-phenyl-but-3-en-2-ol 
• 75-05-8 acetonitrile 
• 99893-78-4 pent-4-en-1-yl 4-chlorobenzoate 
• 67-68-5 dimethyl sulfoxide 
• 2835-77-0 (2-aminophenyl)(phenyl)methanone 
• 2564-83-2 2,2,6,6-tetramethyl-piperidine-N-oxyl 

Downstream Products

• 2564-83-2 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical 
• 2229-07-4 methyl radical 
• 4891-38-7 phenylpropynoic acid methyl ester 
• 103-26-4 Methyl cinnamate 
• 619-50-1 4-nitrobenzoic acid methyl ester 
• 5380-42-7 thiophene-2-carboxylic acid methyl ester 
• 16605-99-5 biphenyl-2-carboxylic acid methyl ester 
• 26537-19-9 methyl 4-tert-butylbenzoate 
• 403-33-8 methyl 4-flurobenzoate 
• 99-75-2 4-methyl-benzoic acid methyl ester 
• 93-58-3 benzoic acid methyl ester 

Relevant academic research and scientific papers

Enantioselective synthesis of epoxides having a tetrasubstituted trifluoromethylated carbon center: Methylhydrazine-induced aerobic epoxidation of β,β-disubstituted enones

The unprecedented title reaction is catalyzed by a methylhydrazine/base/ organocatalyst (1) system. Biologically attractive epoxides (2) having a tetrasubstituted trifluoromethylated carbon center were obtained with excellent enantioselectivity for the first time. 18O-labeling experiments suggest a mechanism involving the activation of molecular oxygen. MTBE=methyl tert-butyl ether. Copyright

Iron-promoted free radical cascade difunctionalization of unsaturated benzamides with silanes

Iron salt/peroxide promoted cascade difunctionalization of unsaturated benzamides with silanes has been reported. It provides a convenient, highly selective, and efficient protocol for the synthesis of various silylated dihydroisoquinolinones and 1,3-isoquinolinediones. In particular, the present methodology only gives cyclization products in good isolated yields under the typical conditions.

Selective Si-C bond cleavage on a diorganosilicon porphyrin complex bearing different axial ligands

Tetraphenylporphyrinato methylphenylsilicon complex (abbreviated to Si(TPP)MePh) was synthesized and structurally characterized. Although the Si-Ph bond of Si(TPP)MePh is much longer than the Si-Me bond, photolysis and chemical oxidation of Si(TPP)MePh cl

Allylic C-H Alkynylation via Copper-Photocatalyzed Cross-Dehydrogenative Coupling

An efficient, novel photocatalyzed allylic-alkynylation methodology via copper-based cross-dehydrogenative coupling (CDC) is described. Different types of 1,4-enyne compounds were synthesized in one step at room temperature using copper(I) terpyridyl comp

Visible-light-promoted catalyst-/additive-free synthesis of aroylated heterocycles in a sustainable solvent

A general visible-light-induced catalyst-/additive-free strategy was developed for the construction of various aroylated heterocycles (55 examples, up to 95% yield, including modification of pharmaceuticals and natural products) such as thioflavones, benzimidazo[2,1-a]isoquinolin-6(5H)-ones, indolo[2,1-a]isoquinolin-6(5H)ones, quaternary 3,3-dialkyl 2-oxindoles, quinoxalin-2(1H)-ones, and benzo[e][1,2,3]oxathiazine 2,2-dioxides in a green solvent (dimethyl carbonate) under air and room temperature conditions. This practical acylation process was achieved using 4-acyl-1,4-dihydropyridines (acyl-DHPs) as acylating reagents under mild conditions, avoiding the use of catalysts, bases, additional oxidants, and traditional organic solvents. This journal is

Non-Heme-Iron-Mediated Selective Halogenation of Unactivated Carbon?Hydrogen Bonds

Oxidation of the iron(II) precursor [(L1)FeIICl2], where L1 is a tetradentate bispidine, with soluble iodosylbenzene (sPhIO) leads to the extremely reactive ferryl oxidant [(L1)(Cl)FeIV=O]+ with a cis disposition of the chlorido and oxido coligands, as observed in non-heme halogenase enzymes. Experimental data indicate that, with cyclohexane as substrate, there is selective formation of chlorocyclohexane, the halogenation being initiated by C?H abstraction and the result of a rebound of the ensuing radical to an iron-bound Cl?. The time-resolved formation of the halogenation product indicates that this primarily results from sPhIO oxidation of an initially formed oxido-bridged diiron(III) resting state. The high yield of up to >70 % (stoichiometric reaction) as well as the differing reactivities of free Fe2+ and Fe3+ in comparison with [(L1)FeIICl2] indicate a high complex stability of the bispidine-iron complexes. DFT analysis shows that, due to a large driving force and small triplet-quintet gap, [(L1)(Cl)FeIV=O]+ is the most reactive small-molecule halogenase model, that the FeIII/radical rebound intermediate has a relatively long lifetime (as supported by experimentally observed cage escape), and that this intermediate has, as observed experimentally, a lower energy barrier to the halogenation than the hydroxylation product; this is shown to primarily be due to steric effects.

Photoinitiated Multicomponent Anti-Markovnikov Alkoxylation over Graphene Oxide

The development of graphene oxide–based heterogeneous materials with an economical and environmentally–friendly manner has the potential to facilitate many important organic transformations but proves to have few relevant reported reactions. Herein, we explore the synergistic role of catalytic systems driven by graphene oxide and visible light that form nucleophilic alkoxyl radical intermediates, which enable an anti-Markovnikov addition exclusively to the terminal alkenes, and then the produced benzyl radicals are subsequently added with N–methylquinoxalones. This photoinduced cascade radical difunctionalization of olefins offers a concise and applicable protocol for constructing alkoxyl–substituted N–methylquinoxalones.

Cu-Catalyzed Oxidative Allylic C-H Arylation of Inexpensive Alkenes with (Hetero)Aryl Boronic Acids

Herein, we present a regioselective Cu-catalyzed oxidative allylic C(sp3)-H arylation by radical relay using a broad range of heteroaryl boronic acids with inexpensive and readily available unactivated terminal and internal olefins. This C(sp2)-C(sp3) allyl coupling has the advantage of using cheap, abundant, and nontoxic Cu2O without the need to use prefunctionalized alkenes, thus offering an alternative method to allylic arylation reactions that employ more traditional coupling partners with preinstalled leaving groups (LGs) at the allylic position.

Ultrafine Copper Oxide Particles Dispersed on Nitrogen-Doped Hollow Carbon Nanospheres for Oxidative Esterification of Biomass-Derived 5-Hydroxymethylfurfural

One-pot synthesis of furan-2,5-dimethylcarboxylate (FDMC) from 5-hydroxymethylfurfural (HMF) is highly demanding for the commercial production of polyethylene furanoate (PEF). Herein, a direct synthesis of FDMC is reported from oxidative esterification of HMF using ultrafine CuO particles dispersed on nitrogen-doped hollow carbon nanospheres (CuO/N?C?HNSs) as a catalyst and tert-butyl hydroperoxide (TBHP) as an oxidizing and methylating reagent. The CuO/N?C?HNSs was prepared through a template protection-sacrifice strategy using SiO2 as a sacrificial template and histidine as the precursor for N and C. N-doping facilitated a strong interaction between the support and copper species, affording formation of CuO nanoparticles of less than 10 nm in size. By virtue of the highly dispersed CuO nanoparticles and a high BET surface area 373 m2/g, the CuO/N?C?HNSsshows excellent catalytic performance in the selective conversion of HMF into FDMC affording 93 % yield of the desired product with a TON value of 49. Furthermore, the oxidative esterification involving SP3C?H bond functionalization is also demonstrated using the same catalyst.

Dual Polymerization Pathway for Polyolefin-Polar Block Copolymer Synthesis via MILRad: Mechanism and Scope

This work explores the mechanism whereby a cationic diimine Pd(II) complex combines coordination insertion and radical polymerization to form polyolefin-polar block copolymers. The initial requirement involves the insertion of a single acrylate monomer into the Pd(II)-polyolefin intermediates, which generate a stable polymeric chelate through a chain-walking mechanism. This thermodynamically stable chelate was also found to be photochemically inactive, and a unique mechanism was discovered which allows for radical polymerization. Rate-determining opening of the chelate by an ancillary ligand followed by additional chain walking allows the metal to migrate to the α-carbon of the acrylate moiety. Ultimately, the molecular parameters necessary for blue-light-triggered Pd-C bond homolysis from this α-carbon to form a carbon-centered macroradical species were established. This intermediate is understood to initiate free radical polymerization of acrylic monomers, thereby facilitating block copolymer synthesis from a single Pd(II) complex. Key intermediates were isolated and comprehensively characterized through exhaustive analytical methods which detail the mechanism while confirming the structural integrity of the polyolefin-polar blocks. Chain walking combined with blue-light irradiation functions as the mechanistic switch from coordination insertion to radical polymerization. On the basis of these discoveries, robust di- and triblock copolymer syntheses have been demonstrated with olefins (ethylene and 1-hexene) which produce amorphous or crystalline blocks and acrylics (methyl acrylate, ethyl acrylate, n-butyl acrylate, and methyl methacrylate) in broad molecular weight ranges and compositions, yielding AB diblocks and BAB triblocks.