76369-03-4

Upstream product

• 22979-35-7 Methyl phenyldiazoacetate 
• 67-63-0 isopropyl alcohol 
• 1179348-58-3 methyl 2-(dimethyl(oxo)-λ⁶-sulfaneylidene)-2-phenylacetate 
• 101-41-7 benzeneacetic acid methyl ester 
• 4358-87-6 (RS)-methyl mandelate 
• 186581-53-3 diazomethane 
• 5394-87-6 (rac)-phenyl(propan-2-yloxy)ethanoic acid 
• 736946-87-5 (R,E)-N-(4-nitrobenzylidene)-2-methylpropane-2-sulfinamide 
• 3230-45-3 (E)-N-benzylidene-2-hydroxyaniline 

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.

Silica-supported HClO4 promotes catalytic solvent- and metal-free O-H insertion reactions with diazo compounds

Solvent-free O-H insertion reactions in the presence of diazo carbonyl compounds were carried-out in very mild conditions. Unlike the traditional metal-catalysed version, employing rhodium acetate dimer, this method uses eco-friendly silica-supported HClO4 as the catalyst. Only 0.3 mol% of this Br?nsted acid catalyst, that can also be recycled several times, is necessary to guarantee very good yields (up to 97%) in the O-H insertion reactions. Reaction set-up is simple and permitted the preparation of forty-three α-hydroxy and α-alkoxy esters/ketones in just 1 h and at room temperature.

Gold (I) catalysis of X-H bond insertions

The utility of gold catalysis for carbene X-H bond insertion chemistry is described for the first time, taking advantage of the unique reactivity of sulfoxonium ylides as metal carbene precursors.

Iridium-catalyzed X-H insertions of sulfoxonium ylides

Image Persented The unique reactivity of sulfoxonium ylides as a carbene source is described for a variety of X-H bond insertions, taking advantage of a simple, commercially available iridium catalyst. This method has applications in both intra- and intermolecular reactivity, including a practical ring-expansion strategy for lactams. The safety and stability of sulfoxonium ylides recommend them as preferable surrogates to traditional diazo ketones and esters.

Stereoselective insertion of rhodium carbenoid to water under control with intramolecular participation of hydroxy group

A chiral diazo ester having a hydroxy group in the proper geometry produces an adduct with water up to 92% de upon treatment with a rhodium catalyst. This high stereoselectivity is attributable to the intramolecular hydrogen bond between the internal hydroxy group and the rhodium carbenoid. Copyright

Water compatible gold(III)-catalysed synthesis of unsymmetrical ethers from alcohols

An efficient and broad-scoped method for the preparation of unsymmetrical ethers from alcohols catalysed by the simplest and least expensive gold catalyst, NaAuCl4, is described for the first time. The procedure enables the etherification of benzylic and tertiary alcohols with moderate to good yields under mild conditions with low catalyst loading. Symmetrical ethers, the usual side products in the etherification of alcohols, were not detected in this case. The formation of the racemic ether from a chiral benzyl alcohol suggests the intermediacy of a carbocation, which has not previously been postulated for gold-catalysed reactions involving alcohols.

Copper(I{cyrillic, ukrainian}) hexafluorophosphate: a dual functional catalyst for three-component reactions of methyl phenyldiazoacetate with alcohols and aldehydes or α-ketoesters

Oxonium ylides in situ generated from methyl phenyldiazoacetate and alcohols in the presence of CuPF6(CH3CN)4 underwent an aldol-type reaction with aldehydes or α-ketoesters in a convergent, three-component fashion to give α-alkoxyl-β-hydroxyl acid derivatives in good yields.

Efficient trapping of oxonium ylides with imines: A highly diastereoselective three-component reaction for the synthesis of β-amino-α-hydroxyesters with quaternary stereocenters

(Chemical Equation Presented) In one huge stride: The single-step construction of polyfunctionalized compounds with a quaternary stereocenter is possible through a highly diastereoselective multicomponent reaction of phenyldiazoacetates, alcohols, and imi

New chiral rhodium(II) carboxylates and their use as catalysts in carbenoid transformations

New chiral dirhodium(II) carboxylates 11-15 have been prepared from the half phthalate esters 6-8 and the pyrroles 9 and 10, and their use as catalysts for the decomposition of diazocarbonyl compounds 16 and 18 investigated.

Carbenes in a Rigid Matrix. Substituent Effects on the Temperature Dependence of α-Carbonylcarbene Reactions

The temperature dependence of methoxycarbonyl- (1a and b) and benzoyl-carbenes (2a and b) reactions in alcohols has been examined in order to elucidate the scope and limitation of low temperature photolysis as a tool for detecting triplet carbenes.The results reveal that the method cannot be applied to all carbenes but gives important information on the reactivity and/or multiplicity of ground-state carbenes.Low-temperature photolysis of PhCN2CO2Me in an ethanol matrix, for example, resulted in a dramatic increase in C-H insertion products, probably derived from the triplet (1a) via an abstraction-recombination mechanism, at the expense of the singlet product, i.e. the O-H insertion compound, which was shown to be the main product of photolysis at ambient temperature.In marked contrast, (1b) generated in a propan-2-ol matrix at -196 deg C did not result in a major increase in the C-H insertion product.Similar and more contrasting substituent effects on the temperature dependence were observed in the benzoylcarbene system (2).Thus, the Wolff rearrangement of (2a) was almost completely supressed in a rigid matrix at -196 deg C, whereas that of (2b) was not appreciably supressed even at -196 deg C.These differences were explained by considering the effects of the substituent on the ground-state multiplicity of carbene and/or on the relation of the activation energy differences of the singlet and triplet reactions with energy differences between two states.