1561-10-0Relevant 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.
supporting information, p. 13848 - 13852 (2018/09/06)
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.
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.