4660-02-0Relevant academic research and scientific papers
Rhodium Porphyrin Catalyzed Regioselective Transfer Hydrogenolysis of C-C σ-Bonds in Cyclopropanes with iPrOH
Chen, Chen,Feng, Shiyu,Chan, Kin Shing
supporting information, p. 2582 - 2589 (2019/07/02)
A new rhodium porphyrin catalyzed regioselective transfer hydrogenolysis of both activated and unactivated cyclopropanes employing iPrOH as the hydrogen source was discovered. The reaction mechanism for the C-C σ-bond activation of cyclopropanes was identified through an initial radical substitution with rhodium(II) metalloporphyrin radical to give a rhodium porphyrin alkyl, followed by hydrogenolysis with iPrOH to give the corresponding acyclic alkanes and regenerate rhodium(II) metalloporphyrin radical.
Highly Diastereo- and Enantioselective Synthesis of Nitrile-Substituted Cyclopropanes by Myoglobin-Mediated Carbene Transfer Catalysis
Chandgude, Ajay L.,Fasan, Rudi
supporting information, p. 15852 - 15856 (2018/11/23)
A chemobiocatalytic strategy for the highly stereoselective synthesis of nitrile-substituted cyclopropanes is reported. The present approach relies on an asymmetric olefin cyclopropanation reaction catalyzed by an engineered myoglobin in the presence of ex situ generated diazoacetonitrile within a compartmentalized reaction system. This method enabled the efficient transformation of a broad range of olefin substrates at a preparative scale with up to 99.9 % de and ee and up to 5600 turnovers. The enzymatic product could be further elaborated to afford a variety of functionalized chiral cyclopropanes. This work expands the range of synthetically valuable, abiotic transformations accessible through biocatalysis and paves the way to the practical and safe exploitation of diazoacetonitrile in biocatalytic carbene transfer reactions.
Towards nitrile-substituted cyclopropanes-a slow-release protocol for safe and scalable applications of diazo acetonitrile
Hock, Katharina J.,Spitzner, Robin,Koenigs, Rene M.
, p. 2118 - 2122 (2017/07/24)
Diazo acetonitrile has long been neglected despite its high value in organic synthesis due to a high risk of explosions. Herein, we report our efforts towards the transient and safe generation of this diazo compound, its applications in iron catalyzed cyclopropanation and cyclopropenation reactions and the gram-scale synthesis of cyclopropyl nitriles.
Olefin cyclopropanations via sequential atom transfer radical addition-dechlorination reactions
Thommes, Katrin,Severin, Kay
, p. 188 - 190 (2011/07/07)
In organic synthesis, cyclopropanation reactions are often performed with Simmons-Smith-type reagents or by transition metal catalyzed reactions of olefins with diazo compounds. A novel method for the synthesis of substituted cyclopropanes is described that is based on a two-step reaction sequence. Olefins are reacted with 1,1'-dichlorides in a Ru-catalyzed atom transfer radical addition (ATRA) process and the resulting 1,3-dichlorides are directly converted into cyclopropanes by reductive coupling with magnesium. This one-pot procedure is applicable to a variety of substrates and can be performed in an inter- or intramolecular fashion. Schweizerische Chemische Gesellschaft.
Olefin cyclopropanation by a sequential atom-transfer radical addition and dechlorination in the presence of a ruthenium catalyst
Thommes, Katrin,Kiefer, Gregor,Scopelliti, Rosario,Severin, Kay
supporting information; experimental part, p. 8115 - 8119 (2010/01/16)
Without diazo: The reductive coupling of olefins with dichloro compounds in the presence of a ruthenium catalyst and magnesium gives cyclopropanes in good yield (see scheme).
Cyclopropanecarbonitriles and their use in perfume compositions
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Page/Page column 3, (2008/06/13)
The present invention is directed to novel cyclopropanecarbonitrile compounds of the general formula wherein R is a hydrogen, or a straight, branched, or cyclic hydrocarbon moiety consisting of 1 to 30 carbon atoms and containing single and/or double bond
VIBRATIONAL CIRCULAR DICHROISM OF OPTICALLY ACTIVE CYCLOPROPANES. 3. TRANS-2-PHENYLCYCLOPROPANECARBOXYLIC ACID DERIVATIVES AND RELATED COMPOUNDS
Yasui, Sritana C.,Keiderling, Timothy A.
, p. 2311 - 2320 (2007/10/02)
Vibrational circular dichroism (VCD) data are presented for a series of (1R,2R)-trans-2-phenyl-1-(R-substituted)cyclopropanes where R=COOCH3, COOCD3, COOH, CONH2, COCl, CN, CH2OH, CD2OD, CH3, CD3, and NH2 (1S,2R).In addition, VCD for (1S,2S)-1-phenylpropylene oxide is presented for comparison.These data can be correlated to show certain characteristic, structure-indicating transitions common to all of the molecules.This is particularly true in the cyclopropane C-H stretching bands in the near-IR and less so of CH2 deformations and ring modes in the mid-IR.To elucidate these comparisons it is necessary to interpret the frerquency shifts of the characteristic bands as the substituent is varied.The range of compounds studied permits such an analysis for certain characteristic modes.The results for monocarbonyl and-cyano substitution further explain the presence and absence, respectively, of coupled oscillator VCD in the corresponding symmetrically disubstituted cyclopropyl compounds.
Steric Retard of Internal Rotation in 1-Carbomethoxy-1,2-diphenylcyclopropane
Doering, W. von E.,Robertson, L. R.,Ewing, E. E.
, p. 4280 - 4286 (2007/10/02)
The high preference (RA = 13) found by Chmurny and Cram for internal rotation of the hydrogen-phenyl carbon bond over the carbomethoxy-phenyl carbon bond in 1-carbomethoxy-1,2-diphenylcyclopropane appears to originate in a steric effect.There b
