10236-10-9Relevant articles and documents
Measuring the Relative Reactivity of the Carbon–Hydrogen Bonds of Alkanes as Nucleophiles
Olmos, Andrea,Gava, Riccardo,Noverges, Bárbara,Bellezza, Delia,Jacob, Kane,Besora, Maria,Sameera, W. M. Chamil,Etienne, Michel,Maseras, Feliu,Asensio, Gregorio,Caballero, Ana,Pérez, Pedro J.
, p. 13848 - 13852 (2018)
We report quantitative measurements of the relative reactivities of a series of C?H bonds of gaseous or liquid CnH2n+2 alkanes (n=1–8, 29 different C?H bonds) towards in situ generated electrophiles (copper, silver, and rhodium carbenes), with methane as the reference. This strategy surpasses the drawback of previous model reactions of alkanes with strong electrophiles suffering from C?C cleavage processes, which precluded direct comparison of the relative reactivities of alkane C?H bonds.
Water as the Reaction Medium for Intermolecular C-H Alkane Functionalization in Micellar Catalysis
álvarez, María,Gava, Riccardo,Rodríguez, Manuel R.,Rull, Silvia G.,Pérez, Pedro J.
, p. 3707 - 3711 (2017)
A series of alkanes CnH2n+2 have been functionalized in water as the reaction medium, using a silver-based catalyst, upon the insertion of carbene (CHCO2Et from N2CHCO2Et) groups into the carbon-hydrogen bonds of hexane, cyclohexane, or 2-methylbutane, among others. The regioselectivity toward the distinct reaction sites is identical to that found in neat alkane, the water-based system allowing the use of a much shorter excess of the hydrocarbon. This is the first example of the intermolecular functionalization of alkanes with this strategy in water. The functionalized alkanes partially undergo the incorporation of a second carbene unit to provide α-(acyloxy)acetates, in an unprecedented tandem reaction of this nature.
Electrochemical cross-coupling of biogenic di-acids for sustainable fuel production
Holzh?user, F. Joschka,Creusen, Guido,Moos, Gilles,Dahmen, Manuel,K?nig, Andrea,Artz, Jens,Palkovits, Stefan,Palkovits, Regina
, p. 2334 - 2344 (2019/05/21)
Direct electrocatalytic conversion of bio-derivable acids represents a promising technique for the production of value-added chemicals and tailor-made fuels from lignocellulosic biomass. In the present contribution, we report the electrochemical decarboxylation and cross-coupling of ethyl hydrogen succinate, methyl hydrogen methylsuccinate and methylhexanoic acid with isovaleric acid. The reactions were performed in aqueous solutions or methanol at ambient temperatures, following the principles of green chemistry. High conversions of the starting materials have been obtained with maximum yields between 42 and 61% towards the desired branched alkane products. Besides costly Pt electrodes also (RuxTi1-x)O2 on Ti electrodes exhibited a notable activity for cross-Kolbe electrolysis. As some of the products are insoluble in water, easy product isolation and reuse of the reaction solvent is enabled via phase separation. Several side products have been identified to evaluate the efficiency of the reaction and to elucidate the factors influencing the product selectivity. The yielded alkanes and esters were assessed with regard to their potential as fuels for internal combustion engines. While the longer alkanes constitute promising candidates for the compression-ignition engine, the smaller ester represents an interesting option for the spark-ignition engine.
