27262-60-8

Upstream product

• 623-73-4 diazoacetic acid ethyl ester 
• 108-94-1 cyclohexanone 

Downstream Products

• 66309-76-0 1-hydroxymethyl-1-cyclohexene-2-carboxylic acid lactone 
• 136707-84-1 Cyclohex-2-en-(E)-ylidene-acetic acid ethyl ester 
• 132723-29-6 2-hydroxy-1-cycloheptenecarboxylate 
• 126580-14-1 ethyl 2-(cyclohex-1-en-1-yl)-2-diazoacetate 
• 774-05-0 ethyl cycloheptanone-2-carboxylate 
• 1557231-90-9 N-(1-(3-cyanobenzyl)-1H-pyrazol-4-yl)-4,5,6,7-tetrahydro-1H-indazole-3-carboxamide 
• 1557248-74-4 C₂₅H₃₂N₆O₂Si 
• 1290045-00-9 ethyl 2-cyclohexylidene-2-(4-methoxy-2-nitrophenyl)acetate 
• 1290044-94-8 ethyl 2-(biphenyl-4-yl)-2-cyclohexylideneacetate 
• 1290044-92-6 ethyl 2-cyclohexylidene-2-(2,3-dimethylphenyl)acetate 
• 1290044-83-5 ethyl 2-cyclohexylidene-2-(4-methoxyphenyl)acetate 
• 1290044-99-3 ethyl 2-cyclohexylidene-2-(naphthalen-1-yl)acetate 
• 1290044-85-7 ethyl 2-cyclohexylidene-2-p-tolylacetate 
• 1290044-88-0 ethyl 2-cyclohexylidene-2-m-tolylacetate 

Relevant academic research and scientific papers

Ethyl Lithiodiazoacetate: Extremely Unstable Intermediate Handled Efficiently in Flow

Ethyl diazoacetate (EDA) is one of the most prominent diazo reagents. It is frequently used in metal–carbene-type reactions. However, EDA can also be used as a nucleophile under base catalysis. Whilst the addition of EDA to aldehydes can be performed using organic bases, the addition of EDA to other carbonyl electrophiles requires the use of organometallics such as lithium diisopropylamide (LDA). The generated ethyl lithiodiazoacetate is highly reactive and decomposes rapidly, even at low temperatures. Herein, we report a continuous flow protocol that overcomes the problems associated with the instantaneous decomposition of ethyl lithiodiazoacetate. The addition of ethyl lithiodiazoacetate to ketones provides direct access to tertiary diazoalcohols in good yields.

Intermolecular [5 + 1]-Cycloaddition between Vinyl Diazo Compounds and tert-Butyl Nitrite to 1,2,3-Triazine 1-Oxides and Their Further Transformation to Isoxazoles

1,2,3-Triazine 1-oxides are formed by nitrosyl addition from tert-butyl nitrite to the vinylogous position of vinyl diazo compounds. This transformation, which is a formal intermolecular [5 + 1] cycloaddition, occurs under mild conditions, with high funct

Visible-light-driven radical 1,3-addition of selenosulfonates to vinyldiazo compounds

Herein, we report a visible-light-driven radical 1,3-selenosulfonylation of vinyldiazo compounds with selenosulfonates, providing various γ-seleno allylic sulfones in good yields. This photochemical reaction was carried out at room temperature in an open flask using ethyl acetate as the solvent without any photocatalysts or additives. The control experiments corroborated that the 1,3-addition proceeded via a radical-chain propagation process. The synthetic applications of the resulting products were demonstrated by deselenization, reduction, bromination and allylation.

Relay Rh(ii)/Pd(0) dual catalysis: Synthesis of α-quaternary β-keto-esters: Via a [1,2]-sigmatropic rearrangement/allylic alkylation cascade of α-diazo tertiary alcohols

A relay Rh(ii)/Pd(0) dual catalysis that enables domino [1,2]-sigmatropic rearrangement/allylic alkylation of α-diazo tertiary alcohols is described. This transformation represents a highly efficient method for the one-pot synthesis of α-quaternary β-keto-esters under mild conditions, in which two separate C-C σ-bonds at the carbenic center were formed in a straightforward manner.

Copper-Catalyzed Oxy-Alkynylation of Diazo Compounds with Hypervalent Iodine Reagents

Alkynes have found widespread applications in synthetic chemistry, biology, and materials sciences. In recent years, methods based on electrophilic alkynylation with hypervalent iodine reagents have made acetylene synthesis more flexible and efficient, but they lead to the formation of one equivalent of an iodoarene as side-product. Herein, a more efficient strategy involving a copper-catalyzed oxy-alkynylation of diazo compounds with ethynylbenziodoxol(on)e (EBX) reagents is described, which proceeds with generation of nitrogen gas as the only waste. This reaction is remarkable for its broad scope in both EBX reagents and diazo compounds. In addition, vinyl diazo compounds gave enynes selectively as single geometric isomers. The functional groups introduced during the transformation served as easy handles to access useful building blocks for synthetic and medicinal chemistry.

Property- and structure-guided discovery of a tetrahydroindazole series of interleukin-2 inducible t-cell kinase inhibitors

Interleukin-2 inducible T-cell kinase (ITK), a member of the Tec family of tyrosine kinases, plays a major role in T-cell signaling downstream of the T-cell receptor (TCR), and considerable efforts have been directed toward discovery of ITK-selective inhibitors as potential treatments of inflammatory disorders such as asthma. Using a previously disclosed indazole series of inhibitors as a starting point, and using X-ray crystallography and solubility forecast index (SFI) as guides, we evolved a series of tetrahydroindazole inhibitors with improved potency, selectivity, and pharmaceutical properties. Highlights include identification of a selectivity pocket above the ligand plane, and identification of appropriate lipophilic substituents to occupy this space. This effort culminated in identification of a potent and selective ITK inhibitor (GNE-9822) with good ADME properties in preclinical species.

Pd-catalyzed coupling of β-hydroxy α-diazocarbonyl compounds with aryl iodides: A migratory insertion/β-hydroxy elimination sequence

The coupling of β-hydroxy α-diazocarbonyl compounds with aryl halides is described, which proceeds through a Pd-catalyzed migratory insertion/β-OH elimination sequence. This reaction provides a new route to the synthesis of tetrasubstituted olefins.

Highly selective catalyst-directed pathways to dihydropyrroles from vinyldiazoacetates and imines

Copper-catalyzed reactions of vinyldiazoacetates with imines occur via a pathway in which the activated imine undergoes electrophilic addition to the vinyldiazo compound, whereas reactions catalyzed by rhodium(II) proceed through a metal carbene to an int

The reaction of α-diazo-β-hydroxy esters with boron trifluoride etherate: Generation and rearrangement of destabilized vinyl cations. A detailed experimental and theoretical study

Cyclic ethyl 2-diazo-3-hydroxy carboxylates were prepared by treating ethyl diazoacetate with LDA followed by reaction with a series of cyclic ketones. Further treatment of these α-diazo-β-hydroxy esters with boron trifluoride etherate in various solvents affords an unusual array of products. Product types and ratios were found to be strongly dependent on ring size and the solvent used. The reaction proceeds by Lewis acid complexation of the alcohol functionality of the diazo hydroxy ester with BF3 etherate followed by neighboring-group participation of the diazo moiety to generate a cycloalkylidene diazonium salt. Loss of nitrogen produces a highly reactive, destabilized, linear vinyl cation. Ring expansion via a 1,2-methylene shift leads to the formation of a more stable, bent cycloalkenyl vinyl cation. A subsequent 1,2-methylene shift results in ring contraction ultimately leading to a stable allylic cation. This cation is either trapped by the solvent or else undergoes cyclization with the adjacent ester group to give a lactone. Computational studies at the 6-31G* level were performed to determine the geometry of the optimized vinyl cations. Relative energies suggest a moderate energy gain for isomerization of the initial vinyl cation V1 to the rearranged vinyl cation V2 followed by a large stabilization in energy for subsequent conversion to the allyl cation A1. Compared with isolated product distributions, the energy profiles suggest kinetically-controlled V1 → V2 → A1 migrations. Finally, the calculations suggest that in diethyl ether the carbocations may be coordinated to a molecule of solvent resulting in "protected" cationic intermediates with nonlinear geometries.

Reaction of Carbonyl Compounds with Ethyl Lithiodiazoacetate. Studies Dealing with the Rhodium(II)-Catalyzed Behavior of the Resulting Adducts

The carbenoid intermediate derived by treating ethyl 2-diazo-4-phthalimidobutyrate with rhodium(II) octanoate undergoes transannular cyclization onto the adjacent imido carbonyl group.The resulting cyclic carbonyl ylide diploe was trapped with several dipolarophiles.In an attempt to prepare related substrates for cyclization studies, the reaction of ethyl lithiodiazoacetate with various aldehydes and ketones was studied.Treatment of the α-diazo-β-hydroxy ester derived from acetone or cyclopentanone with rhodium(II) octanoate gave rise to a β-keto ester.The exclusive phenyl shift encountered with acetophenone is in keeping with migration to an electron-deficient center.The reaction works well with acrolein, leading to high yields of 3-oxo-4-pentenoate.The 1,2-hydrogen shift pathway was found to proceed much faster than intramolecular cyclopropanation.Dehydration of the α-diazo-β-hydroxy esters generates vinyl diazo esters, which readily cyclize to 1H-pyrazoles on thermolysis.