Catalytic hydrogen atom transfer to alkenes: a roadmap for metal hydrides and radicals

Abstract

Hydrogen atom transfer from a metal hydride (MHAT) has emerged as a powerful, if puzzling, technique in chemical synthesis. In catalytic MHAT reactions, earth-abundant metal complexes generate stabilized and unstabilized...

Highly chemoselective synthesis of hindered amides via cobalt-catalyzed intermolecular oxidative hydroamidation

“…5 ), as well as literature reactions between peroxides and relevant Co(II) complexes 62 . It has been proposed that Co(III) species bearing a silicophilic ligand such as an alkoxide or fluoride could react with a silane to give a Co−H species 11 , although the mechanistic pathways of the hydride transfer are not clear 50 . Therefore, it is expected that 9 could behave similarly to give a Co−H species 11 , which then undergoes HAT with an alkene 2 in a reversible fashion.…”

Generation of α‐Boryl Radicals by H. Transfer and their Use in Cycloisomerizations

“…Chemie Communications 22680 www.angewandte.org mechanism for the generation of a-boryl radicals from vinyl boronates. [21] The cyclized alkyl boronates, such as 2 s, offer a platform for late-stage functionalization of 5-membered-ring heterocyclic products. For example, 1) 2 s can be easily oxidized to an alcohol with peroxides; [22] 2) Aggarwals lithiation method [23] can install a furan substituent on the scaffold of 2 s; 3) 2 s can be converted into its more stable BF 3 K salt, which can be used for subsequent Suzuki cross-coupling reactions.…”

Generation of α‐Boryl Radicals by H. Transfer and their Use in Cycloisomerizations

“…Chemie Zuschriften 22862 www.angewandte.de mechanism for the generation of a-boryl radicals from vinyl boronates. [21] The cyclized alkyl boronates, such as 2 s, offer a platform for late-stage functionalization of 5-membered-ring heterocyclic products. For example, 1) 2 s can be easily oxidized to an alcohol with peroxides; [22] 2) Aggarwals lithiation method [23] can install a furan substituent on the scaffold of 2 s; 3) 2 s can be converted into its more stable BF 3 K salt, which can be used for subsequent Suzuki cross-coupling reactions.…”