59123-41-0Relevant articles and documents
Regiodivergent Hydroborative Ring Opening of Epoxides via Selective C-O Bond Activation
Magre, Marc,Paffenholz, Eva,Maity, Bholanath,Cavallo, Luigi,Rueping, Magnus
supporting information, p. 14286 - 14294 (2020/09/15)
A magnesium-catalyzed regiodivergent C-O bond cleavage protocol is presented. Readily available magnesium catalysts achieve the selective hydroboration of a wide range of epoxides and oxetanes yielding secondary and tertiary alcohols in excellent yields and regioselectivities. Experimental mechanistic investigations and DFT calculations provide insight into the unexpected regiodivergence and explain the different mechanisms of the C-O bond activation and product formation.
SUBSTITUTED-QUINOXALINE-TYPE-PIPERIDINE COMPOUNDS AND THE USES THEREOF
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Page/Page column 285, (2009/04/25)
The invention relates to Substituted-Quinoxaline-Type Piperidine Compounds, compositions comprising an effective amount of a Substituted-Quinoxaline-Type Piperidine Compound and methods to treat or prevent a condition, such as pain, comprising administeri
Acid-Catalyzed Olefin-Alcohol Interconversion in the 1-Methylcyclooctyl System. Strain-Relief Acceleration of the Hydration of 1-Methyl-trans-cyclooctene
Chiang, Y.,Chwang, W. K.,Kresge, A. J.,Powell, M. F.,Szilagyi, S.
, p. 5218 - 5224 (2007/10/02)
Rates of reaction with aqueous perchloric acid at 25 deg C have been measured for 1-methyl-cis-cyclooctene, 1-methyl-trans-cyclooctene, and their exo isomer, methylenecyclooctane.The only products formed to any significant extent in each of these reactions are 1-methylcyclooctanol and the cis-cycloalkene, but both the trans- and exo-olefins give these products in initially noneequilibrium proportions: / = 1.27 +/- 0.05 at equilibrium, 15.1 +/- 0.9 from the trans-olefin and 0.44 +/- 0.05 from the exo-olefin.This is taken as evidence for the existence of two conformationally different 1-methylcyclooctyl carbocationic intermediates in these reactions, an unstable crown (or twist) cation formed by protonation of the trans-olefin and a (conformationally) stable boat-chair cation formed from the other two olefins and the alcohol.The barrier for interconversion of these two cations is estimated at ΔG(excit.) = 5.3 +/- 0.6 kcal mol-1.The barrier for hydration of either cation to the alcohol is also estimated, by two different methods, at ΔG(excit.) = 3.6 +/- 0.6 kcal mol-1 or 4.3 +/- 0.3 kcal mol-1.The smallness of these barriers suggests that the reaction of tertiary aliphatic carbocations with water in aqueous solution is an essentially unactivated process.These estimates plus the rate and equilibrium constants measured here allow nearly complete free energy characterization of the 1-methylcyclooctyl system.The rates of reaction of the cis- and exo-olefin with the hydronium ion are normal, but strain relief accelerates the rate of the trans-cycloalkene by a factor of 18500.