50639-30-0

Upstream product

• 51110-48-6 glycine isobutyl ester 
• 78-83-1 2-methyl-propan-1-ol 
• 14661-69-9 p-toluenesulfonylhydrazone glyoxylic acid chloride 
• 57053-69-7 glycine isobutyl ester; hydrochloride 
• 59956-48-8 isobutyl 2-bromoacetate 
• 7779-75-1 isobutyl acetoacetate 

Downstream Products

• 13361-35-8 isobutyl chloroacetate 
• 89829-38-9 isobutyl (E)-4-oxo-4-phenylbut-2-enoate 
• 1290610-70-6 C₄₉H₇₇NO₁₃ 
• 13861-97-7 Pantoyllacton 

Relevant academic research and scientific papers

Two Distinct Ag(I)- And Au(I)-Catalyzed Olefinations between α-Diazo Esters and N-Boc-Derived Imines

Metal-catalyzed reactions between α-diazo esters and imines were well-known to yield aziridine derivatives exclusively. This work reports two new olefination reactions between N-Boc-derived (Boc = tert-Butyloxycarbonyl) imines and α-diazo esters with Ag(I) and Au(I) catalysts, respectively. Our mechanistic studies reveal that these new olefinations involve an initial attack of diazo esters on metal/imine complexes to form Mannich-addition intermediates, which subsequently afford α-aryl-β-aminoacrylates via a Roskamp reaction, or to form β-aryl-β-aminoacrylates via the formation of silver carbenes.

A Catalytic Cross-Olefination of Diazo Compounds with Sulfoxonium Ylides

A ruthenium-catalysed cross-olefination of diazo compounds and sulfoxonium ylides is presented. Our reaction design exploits the intrinsic difference in reactivity of diazo compounds and sulfoxonium ylides as both carbene precursors and nucleophiles, which results in a highly selective reaction.

Radical Cation Cyclopropanations via Chromium Photooxidative Catalysis

The chromium photocatalyzed cyclopropanation of diazo reagents with electron-rich alkenes is described. The transformation occurs under mild conditions and features specific distinctions from traditional diazo-based cyclopropanations (e.g., avoiding β-hydride elimination, chemoselectivity considerations, etc.). The reaction appears to work most effectively using chromium catalysis, and a number of decorated cyclopropanes can be accessed in generally good yields.

A simple criterion for gas chromatography/mass spectrometric analysis of thermally unstable compounds, and reassessment of the by-products of alkyl diazoacetate synthesis

Rationale: A principal limitation of gas chromatography (GC) and gas chromatography/mass spectrometry (GC/MS) is the thermal instability of analytes. We propose that the injector and column temperatures should not exceed the atmospheric pressure boiling point, without decomposition, of the highest homologue of the series being analyzed, instead of the time-consuming procedure of obtaining chromatograms using different temperatures. Methods: A series of thermally unstable diazocarbonyl compounds, alkyl diazoacetates (predicted limit of stability approx. 140 °C, the boiling point of ethyl diazoacetate), was selected for GC/MS analysis using standard equipment. Different GC separation conditions were selected so that the retention temperatures of target compounds were both below and above 140°C. Results: Analyzing alkyl diazoacetates within their thermal stability range permitted reanalysis of their typical synthesis by-products. No dialkyl fumarate or maleate impurities, principal decomposition products which have often been reported previously, were found. Instead, alkyl esters of glycolic acid nitrate, O2NOCH 2CO2R, and 'pseudo-dimeric' products, ROCO[C 2H3NO]CO2R, were discovered for the first time. Conclusions: Avoiding the decomposition of thermally unstable organic compounds during GC and/or GC/MS analysis requires estimating their degradation temperature limits. This limit can be estimated as being equal to the atmospheric pressure boiling point of the highest homologue in the homologous series under consideration that does not decompose on boiling. Copyright

Stability of diazocarbonyl compounds under the conditions of gas chromatography and chromatography-mass spectrometry analysis

The gas chromatographic analysis of alkyldiazoacetates N 2CHCO2R (R = CH3 - C4H9), α-aliphatic diazoketones RCOCHN2 (R = C3H 7, C5H11, and C9H19), and aryl-substituted diazoketones Ph (CH2)nCOCHN2 (n = 0-2) is shown to be possible when their retention temperatures are below the boiling points of compounds of this series at atmospheric pressure without decomposition (about 140°C). At higher temperatures occurs partial or complete decomposition of α-diazoketones in chromatographic columns to form ketenes. Among the impurities in the reaction mixtures at the diazotization of corresponding alkyl glycinates were identified for the first time the nitrate esters of glycolic acid O2NOCH2CO2R, as well as the dimeric products. All diazocarbonyl compounds and the impurities were characterized by mass spectra. For the first time their gas chromatographic retention indices were determined. Pleiades Publishing, Ltd., 2012.

NOVEL MACROCYLES AND METHODS FOR THEIR PRODUCTION

There are provided compounds of formula (I) or a pharmaceutically acceptable salt thereof: wherein the variables R1-R3 are as described in the description, said compounds being useful as anti-inflammatory agents with reduced systemic effects.

Spirolactones from Dirhodium(II)-Catalyzed Diazo Decomposition with Regioselective Carbon-Hydrogen Insertion

Dirhodium(II) caprolactamate, Rh2(cap)4, catalyzes diazo decomposition of cycloalkylmethyl diazoacetates which form spirolactones in moderate to high yield by insertion into a tertiary carbon-hydrogen bond.Similar results are obtained with diazoacetates derived from tetrahydropyran-2-methanol and tetrahydrofurfuryl alcohol but not from cyclopropylmethanol.With tetrahydrofuran-3-ylmethyl diazoacetate, Rh2(cap)4 catalysis promotes δ-lactone formation via insertion into the oxygen-activated secondary C-H bond instead of γ-lactone formation by carbene insertion into the unactivated tertiary C-H bond.However, when both 1,5- and 1,6-positions are activated for insertion by adjacent oxygen atoms, as in (2,2-dimethyl-1,3-dioxolan-4-yl)methyl diazoacetate, five-membered ring formation occurs exclusively in Rh2(cap)4-catalyzed reactions, whereas use of dirhodium(II) acetate leads to both insertion products.