81639-95-4Relevant academic research and scientific papers
Nickel-Catalyzed Favorskii-Type Rearrangement of Cyclobutanone Oxime Esters to Cyclopropanecarbonitriles
Fang, Ping,Mei, Tian-Sheng,Shuai, Bin
supporting information, p. 1637 - 1641 (2021/10/02)
A nickel-catalyzed base-promoted rearrangement of cyclobutanone oxime esters to cyclopropanecarbonitriles was developed. The ring opening of cyclobutanone oxime esters occurs at the sterically less hindered side. A base-promoted nickelacyclobutane intermediate, formed in situ, is assumed to be involved in the formation of the product.
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.
supporting information, 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.
The Photochemistry of 1-Cyano-2-methyl-3-phenylpropene and Ring substituted Derivatives
Ferreira, Aurelio B. B.,Salisbury, Kingsley
, p. 25 - 30 (2007/10/02)
The E- and Z-isomers of 1-cyano-2-methyl-3-phenylpropene and ring-substituted derivatives of the E-isomer, are shown to fluoresce and undergo Z-E-isomerization and di-?-methane rearrangement on irradiation.The rate constants for these processes, obtained from fluorescence lifetimes and quantum yields, can be analysed in terms of an initial interaction between the two ? systems, facilitated by partial charge-transfer, followed by two diverging pathways, one, towards a diradicaloid species leading to cyclopropane formation, the other towards a 'zwitterionic' species and relaxation to the ground state and resulting in singlet state Z-E-isommerization.
