6570-83-8Relevant academic research and scientific papers
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 (2017/06/09)
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.
Functionalization of CnH2n+2 Alkanes: Supercritical Carbon Dioxide Enhances the Reactivity towards Primary Carbon-Hydrogen Bonds
Gava, Riccardo,Olmos, Andrea,Noverges, Bárbara,Varea, Teresa,Funes-Ardoiz, Ignacio,Belderrain, Tomás R.,Caballero, Ana,Maseras, Feliu,Asensio, Gregorio,Pérez, Pedro J.
, p. 3254 - 3260 (2015/10/28)
The functionalization of the primary sites of alkanes is one of the more challenging areas in catalysis. In this context, a novel effect has been discovered that is responsible for an enhancement in the reactivity of the primary C-H bonds of alkanes in a catalytic system. The copper complex Cu(NCMe) (=hydrotris{[3,5-bis(trifluoromethyl)-4-bromo]-pyrazol-1-yl}borate) catalyzes the functionalization of CnH2n+2 with ethyl diazoacetate upon inserting the CHCO2Et unit into C-H bonds. In addition, the selectivity of the reaction toward the primary sites significantly increased relative to that obtained in neat alkane upon using supercritical carbon dioxide as the reaction medium. This was attributed to the effect of the carbon dioxide molecules that withdraw electron density from the fluorine atoms of the ligand, which enhances the electrophilic nature of the metal center. DFT studies validated this proposal.
