Homogeneous catalytic C(sp³)–H functionalization of gaseous alkanes

Abstract

The conversion of light alkanes into bulk chemicals is becoming an important challenge as it avoids effectively the use of prefunctionalized alkylating reagents. The implementation of such processes is, however,...

The continuum of carbon–hydrogen (C–H) activation mechanisms and terminology

“…Nonetheless, these explorations are equally important in the pursuit of sustainable methods for hydrocarbon functionalisation. These systems include, but are not limited to, enzymatic reactivity 99 , photocatalysis 100 – 102 , heterogeneous catalysis 103 , 104 , and main group reactivity 105 – 107 . The area of C-H activation and functionalisation continues to be of high interest for the chemical community, presumably because of the fundamental and potentially ground-breaking innovations that have yet to be discovered.…”

Photocatalytic Chlorination of Methane Using Alkali Chloride Solution

“…Due to the inert chemical properties of CH 4 , the functionalization of CH 4 into intermediate chemicals is required for the further transformation into high-value-added products. − Various reaction systems have been developed for methane functionalization under both homogeneous , and heterogeneous conditions. ,, Catalytic methane halogenation, especially chlorination and bromination, is an effective way to increase the utilization value of methane . Methyl chloride (CH 3 Cl) is an important chemical intermediate in the organic chemical industry .…”

Synthetic Applications of Photocatalyzed Halogen‐Radical Mediated Hydrogen Atom Transfer for C−H Bond Functionalization

“…For example, when an acetonitrile solution of cyclohexane (14.1) and dimethyl fumarate (14.2) was irradiated with UV light in the presence of [PPh 4 ] 2 TiCl 6 , product 14.6 was isolated in 74 % yield. Notably, the same transformation could be extended to challenging gaseous alkanes [81] such as ethane (1 atm) to obtain adduct 14.7 and 14.8 in 50 % and 72 % yield. The site-selectivity of the HAT step was also investigated with pentane as the substrate (see compound 14.9) and found to be in accordance with a chlorine radical as the hydrogen abstracting species.…”