10489-28-8Relevant articles and documents
Radical cyclisation onto nitriles
Bowman,Bridge,Brookes
, p. 8989 - 8994 (2000)
Iminyl radicals, generated by 5-exo cyclisation of alkyl, vinyl and aryl C-centred radicals onto nitriles, undergo β-scission (nitrile translocation), reduction or tandem cyclisation onto alkenes depending on the nature of the α-substituent. 5-exo Cyclisations of aryl radicals onto nitriles undergo nitrile translocation when the α-substituent is CN, CO2R, SO2Ph or CONMe2. The rate of translocation is faster than 5- or 6-exo cyclisation onto alkenes or 1,5-hydrogen abstraction of allylic hydrogens. When the α-substituents are alkyl, the intermediate iminyl radicals do not undergo nitrile translocation. (C) 2000 Elsevier Science Ltd.
The generation of aryl anions by double electron transfer to aryl iodides from a neutral ground-state organic super-electron donor
Murphy, John A.,Zhou, Sheng-Ze,Thomson, Douglas W.,Schoenebeck, Franziska,Mahesh, Mohan,Park, Stuart R.,Tuttle, Tell,Berlouis, Leonard E. A.
, p. 5178 - 5183 (2007)
(Chemical Equation Presented) It takes two to cyclize: Aryl halides are reduced to aryl anions by double electron transfer from the neutral ground-state electron donor 1 (see scheme), as shown by the formation of a cyclic ketone (2). The reduced compound (3) is also formed. Calculations show that the loss of two electrons from 1 is both thermodynamically and kinetically viable and generates a more planar resonance-stabilized structure.
Process chemistry related to the experimental rice herbicide 2,2-dimethyl-1-(4-methylthio-5-pyrimidinyl)indane
Dietsche, Thomas J.,Gorman, David B.,Orvik, Jon A.,Roth, Gary A.,Shiang, William R.
, p. 275 - 285 (2000)
Two concise syntheses of the experimental rice herbicide 2,2-dimethyl-1-(4-methylthio-5-pyrimidinyl)indane are reported. The initial synthesis relies on a low-temperature addition of 5-lithio-4-methylthiopyrimidine to 2,2-dimethyl-1-indanone to construct the pyrimidinylindane system. Process improvements to this route are described and resulted in the preparation of 90 kg of the title compound on pilot plant scale. Economics dictated the need to identify a new synthetic route which utilized inexpensive raw materials. Detailed herein is the initial discovery of a new route which features a novel combination of dissolving metal reduction/formylation/cyclization to construct the requisite pyrimidine ring. Process improvements to this chemistry have allowed us to deliver an appropriately substituted pyrimidinylindane in a minimal number of synthetic operations.
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Schiavelli,M.D. et al.
, p. 3054 - 3055 (1973)
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Nickel-Catalyzed Domino Heck-Type Reactions Using Methyl Esters as Cross-Coupling Electrophiles
Zheng, Yan-Long,Newman, Stephen G.
supporting information, p. 18159 - 18164 (2019/11/13)
While esters are frequently used as traditional electrophiles in substitution chemistry, their application in cross-coupling chemistry is still in its infancy. This work demonstrates that methyl esters can be used as coupling electrophiles in Ni-catalyzed Heck-type reactions through the challenging cleavage of the C(acyl)?O bond under relatively mild reaction conditions at either 80 or 100 °C. With the σ-NiII intermediate generated from the insertion of acyl NiII species into the tethered C=C bond, carbonyl-retentive products were formed by domino Heck/Suzuki–Miyaura coupling and Heck/reduction pathways when organoboron and mild hydride nucleophiles are used.
Potent Inhibitors of Plasmodial Serine Hydroxymethyltransferase (SHMT) Featuring a Spirocyclic Scaffold
Schwertz, Geoffrey,Witschel, Matthias C.,Rottmann, Matthias,Leartsakulpanich, Ubolsree,Chitnumsub, Penchit,Jaruwat, Aritsara,Amornwatcharapong, Watcharee,Ittarat, Wanwipa,Sch?fer, Anja,Aponte, Raphael A.,Trapp, Nils,Chaiyen, Pimchai,Diederich, Fran?ois
supporting information, p. 931 - 943 (2018/04/20)
With the discovery that serine hydroxymethyltransferase (SHMT) is a druggable target for antimalarials, the aim of this study was to design novel inhibitors of this key enzyme in the folate biosynthesis cycle. Herein, 19 novel spirocyclic ligands based on