930-89-2Relevant articles and documents
Electrochemical Coupling of Biomass-Derived Acids: New C8 Platforms for Renewable Polymers and Fuels
Wu, Linglin,Mascal, Mark,Farmer, Thomas J.,Arnaud, Sacha Pérocheau,Wong Chang, Maria-Angelica
, p. 166 - 170 (2017/01/17)
Electrolysis of biomass-derived carbonyl compounds is an alternative to condensation chemistry for supplying products with chain length >C6for biofuels and renewable materials production. Kolbe coupling of biomass-derived levulinic acid is used to obtain 2,7-octanedione, a new platform molecule only two low process-intensity steps removed from raw biomass. Hydrogenation to 2,7-octanediol provides a chiral secondary diol largely unknown to polymer chemistry, whereas intramolecular aldol condensation followed by hydrogenation yields branched cycloalkanes suitable for use as high-octane, cellulosic gasoline. Analogous electrolysis of an itaconic acid-derived methylsuccinic monoester yields a chiral 2,5-dimethyladipic acid diester, another underutilized monomer owing to lack of availability.
A structure-activity study of Ni-catalyzed alkyl-alkyl kumada coupling. Improved catalysts for coupling of secondary alkyl halides
Ren, Peng,Vechorkin, Oleg,Von Allmen, Kim,Scopelliti, Rosario,Hu, Xile
supporting information; experimental part, p. 7084 - 7095 (2011/06/26)
A structureactivity study was carried out for Ni catalyzed alkylalkyl Kumada-type cross coupling reactions. A series of new nickel(II) complexes including those with tridentate pincer bis(amino)amide ligands (RN2N) and those with bidentate mixed amino-amide ligands (RNN) were synthesized and structurally characterized. The coordination geometries of these complexes range from square planar, tetrahedral, to square pyramidal. The complexes had been examined as precatalysts for cross coupling of nonactivated alkyl halides, particularly secondary alkyl iodides, with alkyl Grignard reagents. Comparison was made to the results obtained with the previously reported Ni pincer complex [( MeN2N)NiCl]. A transmetalation site in the precatalysts is necessary for the catalysis. The coordination geometries and spin-states of the precatalysts have a small or no influence. The work led to the discovery of several well-defined Ni catalysts that are significantly more active and efficient than the pincer complex [(MeN2N)NiCl] for the coupling of secondary alkyl halides. The best two catalysts are [(HNN)Ni(PPh3)Cl] and [(HNN)Ni(2,4-lutidine)Cl]. The improved activity and efficiency was attributed to the fact that phosphine and lutidine ligands in these complexes can dissociate from the Ni center during catalysis. The activation of alkyl halides was shown to proceed via a radical mechanism.
EVIDENCE FOR A SINGLE ELECTRON TRANSFER MECHANISM IN REACTIONS OF LITHIUM DIORGANOCUPRATES WITH ORGANIC HALIDES
Ashby, E. C.,DePriest, R. N.,Tuncay, A.,Srivastava, Sushil
, p. 5251 - 5254 (2007/10/02)
It has been demonstrated by means of spectroscopic studies involving cyclizable alkyl halides that lithium dimethylcuprate can react with organic halides by a single electron transfer pathway.
