Synthesis, Characterization, and Reactivity of a Hypervalent‐Iodine‐Based Nitrooxylating Reagent

Abstract

Herein, the synthesis and characterization of a hypervalent‐iodine‐based reagent that enables a direct and selective nitrooxylation of enolizable C−H bonds to access a broad array of organic nitrate esters is reported. This compound is bench stable, easy‐to‐handle, and delivers the nitrooxy (‐ONO2) group under mild reaction conditions. Activation of the reagent by Brønsted and Lewis acids was demonstrated in the synthesis of nitrooxylated β‐keto esters, 1,3‐diketones, and malonates, while its activity under photoredox catalysis was shown in the synthesis of nitrooxylated oxindoles. Detailed mechanistic studies including pulse radiolysis, Stern–Volmer quenching studies, and UV/Vis spectroelectrochemistry reveal a unique single‐electron‐transfer (SET)‐induced concerted mechanistic pathway not reliant upon generation of the nitrate radical.

Aza‐oxyallyl Cations and Their Applications in (3+m) Cycloaddition Reactions

“…Cyclic λ 3 ‐iodanes, for example, ethynylbenziodoxolones (EBXs) is used as versatile electrophilic group transfer reagent [25a–b] . Due to synthetic applicability various modified EBXs have been synthesized [25c] . Very recently Kang et al.…”

Synthesis, Characterization of Spirocyclic λ3‐Iodanes and Their Application to Prepare 4,1‐Benzoxazepine‐2,5‐diones and 1,3‐Diynes

“…For example, the cyclic iodine(III) (called as λ 3 ‐iodane) containing acetate, halogens, trifluoromethyl, azides, cyanides, aryl and alkyl groups, [1h, 2] were reported by the pioneering groups, such as, Waser, Zhdankin, Kita, Beringer, Koser, Valvoglis, Moriarty, Ochiai, and Togni [1, 2] . More recently, two type of cyclic λ 3 ‐iodanes containing a (diarylmethylene)amino and nitrooxy groups were reported by the group of Kiyokawa, Minakata [2e] and Katayev, [2f] respectively.…”

Palladium-catalyzed C(sp3)–H nitrooxylation of masked alcohols

“…9 A photocatalytic approach has also been reported with the help of a novel high-valent iodine derivative. 10 Despite the successes achieved in the above-mentioned methods, methods to synthesize organic nitrates in a more efficient and straightforward way are still needed.…”