Measuring the Relative Reactivity of the Carbon–Hydrogen Bonds of Alkanes as Nucleophiles. Issue 42 (23rd August 2018)

• Record Type: Journal Article
• Authors: 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.
• Is Part Of: Angewandte Chemie international edition. Volume 57:Issue 42(2018)
• Page Start: 13848
• Page End: 13852
• Publication Date: 2018-08-23
• Subjects: alkanes -- C−H bond functionalization -- electrophilicity -- metal carbene complexes -- nucleophilicity; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201807448
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: We report quantitative measurements of the relative reactivities of a series of C−H bonds of gaseous or liquid C n H2 n +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. Abstract : The relative reactivities of the C−H bonds of alkanes, C n H2 n +2, acting as nucleophiles are reported, and range from n =1 (methane as the reference) to n =8 towards several silver, copper, or rhodium carbene complexes acting as strong electrophiles. The data collected evidence the lack of a general trend for the reaction sites in intermolecular processes.