Copper-Catalyzed N–H/C–H Sequential Relay Oxidative Radical Carboannulation: Construction of Diversely Substituted [60]Fullerene-Fused Tetrahydrocyclopenta[b]indoles

Abstract

Reported herein is a new copper-catalyzed N−H/C−H sequential relay oxidative radical carboannulation of [60]fullerene with C2-functionalized free indoles for the direct construction of novel [60]fullerene-fused tetrahydrocyclopenta-[b]indoles. The transformation shows high regioselectivity and atom economy, broad substrate scope, and good functional group tolerance, providing an efficient and practical approach to access diversely substituted fullerene-fused polycyclic derivatives from simple hydrocarbons.

Cu(I)-Catalyzed Synthesis of [60]Fullerene-Fused Lactams and Further Electrochemical Functionalization

“…Metal salts including Mn­(III), Fe­(II)/Fe­(III), Co­(II), Ni­(II), Pd(0)/Pd­(II), and Ag­(I) have been widely employed to construct various C 60 derivatives. Copper salts have also been widely used in fullerene chemistry and still remain as attractive promoters, because they are inexpensive, less toxic, and readily available.…”

Transition-Metal-Free Domino Reaction of [60]Fullerene, Indole, and DMSO/HCl: One-Pot Access to Diverse N-Substituted [60]Fulleroindole Derivatives

“…FT-IR (KBr): v 3398, 2912, 1703, 1619, 1541, 1509, 1459, 1425, 1353, 1326, 1253, 1212, 1168, 1031, 908, 853, 795, 762, 704, 575, and N-Substituted [60]Fulleroindole 2i. According to the general procedure, the reaction of C 60 (36.0 mg, 0.05 mmol) with 1i (9 mg, 0.06 mmol) and KO t Bu (11.2 mg, 0.1 mmol) afforded first unreacted C 60 (18.7 mg, 52%) and then 2i (14.0 mg, 32%) as an amorphous black solid: mp > 300 °C; 1 H NMR (400 MHz, CS 2 /DMSO-d 6 ): δ 8.19 (s, 1H), 7.89 (s, 1H), 7.68 (d,J = 8.8 Hz,1H),7.11 (s,1H), 7.06 (d,J = 8.8 Hz,1H),6.40 (t,J = 8.0 Hz,1H),5.65 (d,J = 7.2 Hz,2H), and 4.01 (s, 3H). 13 C{ 1 H} NMR (100 MHz, CS 2 /DMSO-d 6 ) (all 2C unless indicated): δ 154.…”

NHC-Catalyzed Three-Component Hydroalkylation Reactions of [60]Fullerene: An Umpolung Approach to Diverse Monoalkylated Hydrofullerenes

“…Ye and co-workers recently established NHC-catalyzed ε-functionalization via the p -quinodimethane intermediate . Inspired by these pioneering works, and our continuous interest in catalytic functionalization of [60]­fullerene, , we herein report the first example of organocatalytic hydroalkylation of [60]­fullerene with 4-(chloromethyl)-benzaldehydes/α,β-unsaturated aldehydes and alcohols/thioalcohols. Notably, by means of this novel NHC-catalyzed three-component umpolung methodology, a series of novel hydroalkylation derivatives can be flexibly and efficiently prepared in a highly selective manner with a wide substrate scope and excellent functional group tolerance.…”