Copper Nitrate‐Mediated Selective Difunctionalization of Alkenes: A Rapid Access to β‐Bromonitrates

Abstract

A regioselective copper nitrate‐mediated difunctionalization of alkenes has been developed for the rapid synthesis of β‐bromonitrates, where copper nitrate is used as an ideal nitrooxy source for the first time and the products will find many applications in organic synthesis as versatile synthons. Different from the general reports that copper nitrate acts as the nitro source, the given protocol provides a direct access to functionalized nitrates, with operational simplicity, good functional group tolerance and a wide substrate scope.magnified image

Copper Nitrate Mediated Regioselective Difunctionalization of Alkenes with N-Fluorobenzenesulfonimide: A Direct Approach to β-Aminonitrates

“…17b Also, a difunctionalization reaction of alkenes with copper nitrate and N -bromo­succinimide was developed to afford β-bromonitrates efficiently, where copper nitrate serves as the nitrate source (Scheme 1a ). 17d On the basis of the precedent works, we envisioned copper nitrate may provide a nitrate moiety to react with a C-centered radical intermediate generated in situ by copper-mediated reaction of NFSI with alkenes, thus leading to a new difunctionalization of alkenes. To this end, we herein report a regioselective oxyamination reaction of alkenes by utilizing copper nitrate as the nitrate source and NFSI as the nitrogen source (Scheme 1b ).…”

Simple and Versatile Nitrooxylation: Noncyclic Hypervalent Iodine Nitrooxylating Reagent

“…In these protocols, the activations of C−H bond were limited at β‐methyl group and the directing group in the substrates were required. In addition, transition‐metal nitrate salts such as copper nitrate [16] and ferric nitrate nonahydrate [17] have been used as nitrate source for nitrooxylations.…”

From Alkenes to Isoxazolines via Copper-Mediated Alkene Cleavage and Dipolar Cycloaddition

“…Isocyanide induced activation of copper sulfate is recently disclosed by our group, affording sulfonic esters through C–H sulfonation . Besides, copper nitrate has been proven to be a common and versatile reagent for the synthesis of nitro compounds, nitrates, and heterocycles …”