Ir-Catalyzed cyclization of α,ω-dienes with an N-methyl group via two C–H activation steps

Abstract

Iridium-catalyzed sp3 C–H alkylation of an N-methyl group with 1,5- and 1,6-dienes proceeded to give five- and six-membered carbocyclic compounds, respectively, in high yields. The reaction involves intermolecular alkylation of...

Iridium-Catalyzed Enantioselective Direct α-C–H Alkylation of Saturated Cyclic Amines with Alkenes

“…Transition-metal-catalyzed enantioselective direct α-C­(sp 3 )–H functionalization, which realizes a step and atom economical process, has been demonstrated as an alternative way to construct chiral α-functionalized cyclic amines. , Although the functionalization of α-C­(sp 3 )–H bonds adjacent to nitrogen has been achieved by Ru, Rh, and Ir catalysts to build new C–C bonds with alkenes and alkynes, − enantioselective α-C­(sp 3 )–H alkylation of saturated azacycles has been underdeveloped . In this respect, Shibata and co-workers reported Ir-catalyzed asymmetric alkylation of γ-butyrolactam bearing a pyridyl group as the directing group with styrenes or electron-deficient alkenes to give 5-substituted γ-lactams with high enantioselectivity .…”

Asymmetric addition of an N-methyl C(sp3)–H bond to cyclic alkenes enabled by an iridium/phosphine–olefin catalyst

“…1 In this respect, the functionalization of C(sp 3 )–H bonds is still challenging because of the low reactivity. 2 The C(sp 3 )–H bond adjacent to nitrogen atom is relatively reactive toward transition metals, 3 and the addition reaction to unsaturated bonds has been realized by the use of ruthenium, 4 rhodium, 5 and iridium 6,7 catalysts. Mono-substituted terminal alkenes have often been applied to those reactions, while the use of multiply-substituted alkenes is still limited.…”