Copper-mediated domino C–H iodination and nitration of indoles

Abstract

An efficient and cost-effective copper-mediated aerobic oxidative C-H iodination and nitration of indoles via double C-H functionalization is reported. The domino process proceeds smoothly under mild aerobic conditions to give 3-iodo-2-nitroindoles in one step with high regioselectivity and a broad substrate scope. The mechanism of the iodination step is proposed to proceed via a Cu(iii)-iodide species that undergoes electrophilic addition at the C3 position of the indole motif. The subsequent nitration step involves a sequence of C-H activation, nitro radical oxidative addition, and reductive elimination.

Recent Advances in Copper‐Catalyzed C−N Bond Formation Involving N‐Centered Radicals

“…In 2018, Jiang and co‐workers reported a cost‐effective and practical method for the construction of 3‐iodo‐2‐nitroindoles in one step via a Cu‐mediated aerobic oxidative C−H iodination and nitration of indoles featuring a direct group (Scheme 47). [63] When CuBr was used instead of CuI, the tandem bromination/nitration reaction enabled the facile synthesis of the 3‐bromo‐2‐nitroindole product featuring an N ‐2‐pyrimidine directing group in 68 % with high regioselectivity. N ‐pyri(mi)dyl indoles bearing electron‐donating (e. g., Me and OMe) and electron‐withdrawing groups (e. g., F, Cl, and CN) on the phenyl ring were all well tolerated.…”

Recent Advances in Transition-Metal-Catalyzed Directing Group Assisted Nitration of Inert C-H Bonds

“…2015 年, 燕红等 [27] 2018 年, 姜超等 [36] 2017 年, 郭凯等 [44] 以亚硝酸叔丁酯为硝基源、廉价 的镍盐作为催化剂, 有效地实现了 2-芳基噁唑啉酰胺底 物远程 C-H 键硝化反应(Eq. 30).…”

Biomedical Applications of Fluorescent and Magnetic Resonance Imaging Dual‐Modality Probes

“…[15,25] Al iposomec ontainingacombination of paramagnetic Gd-DTPA-bis(stearylamide) (Gd-DTPA-BSA) and fluorescent FITC hasb een applied to detect cell apoptosis in vivo. [26] Other fluorescent dyes, such as rhodamine [27] and its derivatives, [16c, 28] Oregon Green 488, [29] naphthylamine (Nap), [30] naphthalimide, [31] spirobenzopyran, [32] [Ru(bpy) 3 ]Cl 2 (bpy:2 ,2'-bipyridine), [25] and [Re(bpy)(CO) 3 ], [33] in combination with ag adolinium complex have been used as a bifunctional probe to yield dual-modality imaging CAs with great promise in vitro and in vivo. [27] As shown in Figure 1, a special gadolinium compound, Nap-DO3A-Gd, consisting of a Nap luminescentm oiety,a1,4,7,10 tetraazacyclododecane-1,4,7-triacetic acid (DO3A)c omponent,a nd ad i-2-picolylamine (DPA) binding chelator was developed as ab ifunctional probe for selectivef luorescent sensing and MRI of Cu 2 + in vitro.…”