Functional-group translocation of cyano groups by reversible C–H sampling

Recent advances of decatungstate photocatalyst in HAT process

“…Xu et al 68 discovered a functional-group translocation reaction of cyano (CN) groups in common nitriles that allows a direct positional exchange between an unactivated C–H bond and a CN group. High fidelity for 1,4-CN translocation was shown by the reaction, which is frequently in contrast to the inherent selectivity of sites in conventional C–H functionalizations.…”

Radical-triggered base-free 1,3-C → C migrations: chemodivergent synthesis of cyclic imines from N-allyl enamines

“…The thermal isomerization of vinylcyclopropanes to cyclopentenes is the typical 1,3-C → C migration, and was first reported in 1960 (Scheme 1a). 12,13 Recently, transition-metal catalyzed 1,3-alkynyl, 14 vinyl, 15 (hetero)aryl, 16 aza-benzyl 17 and cyano 18,19 migrations have been developed from and limited to alkynyl alkenyl carbinol or allylic alcohols, affording versatile ketones (Scheme 1b). In these [1,3]-migrations, the use of one or more equivalents of base or high temperature was unavoidable, since the activation of the O-H bond is essential for the cleavage of the adjacent C-C bonds via β-scission.…”

Terminal C(sp 3 )–H borylation through intermolecular radical sampling

“…The second pathway begins with an unselective HAT step, leading to the formation of both primary and secondary radicals, followed by a radical sampling procedure ( 22 ) to realize the formation of terminal-functionalized product. The unreactive secondary radicals revert to the substrate molecules through the reverse HAT reaction (Fig.…”