Preparation of Organic Nitrates from Aryldiazoacetates and Fe(NO₃)₃·9H₂O

Abstract

A thermal protocol is reported for the formal insertion of nitric acid into aryldiazoacetates using Fe(NO 3 ) 3 • 9H 2 O. This strategy is mild and high yielding and allows the preparation of a large variety of members of an unprecedented family of organic nitrates. The nitrate group can be also readily transformed into other functional groups and heterocyclic moieties and can possibly allow new biological explorations of untapped potential associated with their NO-releasing ability.

Iron‐Promoted Radical Cyclization of β, γ‐Unsaturated Oximes: Dual Role of Iron(III) Nitrate as a Promoter and Nitrooxy Source

“…Based on the control experiments and previous reports, [9,12,15] a plausible mechanism for the cyclization of β,γunsaturated oximes is proposed in Scheme 5. First, unsaturated oxime 1 a interacts with Fe(NO 3 ) 3 to generate radical species A through a single electron oxidation process with the formation of Fe(II).…”

“…For example, Jurberg's group recently synthesized organic nitrates under mild reaction conditions using aryldiazoacetates as the substrates and Fe(NO 3 ) 3 • 9H 2 O as the nitrooxy source (Scheme 1b). [12] Based on these considerations, we assumed that the application of Fe(NO 3 ) 3 • 9H 2 O would be extended to a more significant chemical transformation. As one part of our continuous efforts on the functionalization of β,γ-unsaturated oximes, [13b-d] we herein disclosed a rare iron(III)-mediated nitrooxylation reaction of β,γ-unsaturated oximes to access isoxazo-lines that feature a nitrooxy substituent, where Fe(NO 3 ) 3 • 9H 2 O acts as a promoter and a nitrooxy source (Scheme 1c).…”

“…However, only few examples regarding the use of Fe(NO 3 ) 3 ⋅ 9H 2 O as the nitrooxy source are reported, where nucleophilic substitution reactions involving NO 3 − are supported for the desired chemical events. For example, Jurberg's group recently synthesized organic nitrates under mild reaction conditions using aryldiazoacetates as the substrates and Fe(NO 3 ) 3 ⋅ 9H 2 O as the nitrooxy source (Scheme 1b) [12] . Based on these considerations, we assumed that the application of Fe(NO 3 ) 3 ⋅ 9H 2 O would be extended to a more significant chemical transformation.…”

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

“…Further methodologies include a CAN‐mediated radical alkylation, which although interesting from a mechanistic standpoint, presents limited synthetic applicability and scope . More recently, a CAN‐mediated benzylic nitrooxylation, and the formal insertion of HNO 3 into aryldiazoacetates have been described.…”

Synthese, Charakterisierung und Reaktivität eines Nitrooxylierungsreagenzes basierend auf einer hypervalenten Iodverbindung

“…Ein mechanistisch interessanter Zugang stellt die CAN-vermittelte radikalische Alkylierung dar,die jedoch eingeschränkte synthetische Nutzbarkeit und geringe Substratbreite aufweist. [20] Kürzlich wurden auch Methoden zur CAN-vermittelte Nitrooxylierung der Benzylposition [21] sowie die formale Insertion von Salpetersäure in Aryldiazoace-tate [22] beschrieben. Die Entwicklung eines unter konventionellen Laborbedingungen handhabbaren Reagenzes,d as die direkte Übertragung der NO 3 -Gruppe auf eine Breite von Substraten unter milden Bedingungen erlaubt und nicht auf der Verwendung vorfunktionalisierter Ausgangsverbindungen oder stark oxidierender Reaktionsbedingungen beruht, stellt eine wesentliche Hürde dar, um den breiten synthetischen Zugang zu neuen organischen Nitraten mit bisher unbekannten Eigenschaften zu ermçglichen.…”