Development of Nitrolactonization Mediated by Iron(III) Nitrate Nonahydrate

Abstract

The nitrolactonization of alkenyl carboxylic acids mediated by Fe(NO 3) 3 •9H 2 O has been developed. Nitrolactones were obtained in up to 93% yield by treatment of alkenyl carboxylic acids with Fe(NO 3) 3 •9H 2 O. Mechanistic studies disclosed that the reaction proceeded through a radical intermediate generated from addition of NO 2 to alkenyl carboxylic acids.

Nitryl Radical‐Triggered Semipinacol‐Type Rearrangement, Lactonization, and Cycloetherification of Olefins

“…The development of synthetic methods to introduce NO 2 ‐containing lactones has attracted our attention owing to the limited literature reports available to date. As of now, only nitro lactonization by ferric nitrate is known at high reaction temperatures, [43] thus a milder protocol can serve as a beneficial entry to synthesize nitro‐containing lactones. Using our simple and room temperature protocol, we speculated that readily available olefinic acids can undergo the nitro lactonization reaction to access cyclic systems with oxa‐carbon quaternary center motif.…”

Electron‐Driven Nitration of Unsaturated Hydrocarbons

“…Adducts with α-substituents (32-36), reacted decently, regardless of their steric and electronic nature. Various 1,2-disubstitued styrenes bearing a wide variety of acid-sensitive functionalities performed well under electrochemical conditions (37)(38)(39), while the presence of a carbonyl group at olefin β-center makes the reaction sluggish (41)(42)(43). The structure of compound 40 was unambiguously demonstrated by single-crystal X-ray crystallography.…”

“…[41] When 4-phenylpent-4-enoic acid or 2-(1phenylvinyl)benzoic acid were exposed to electrochemical conditions, nitrative lactonization takes place, affording γlactones 81 and 82, respectively (Scheme 5B). [42] Next, we investigated the possibility of introducing nitro group via ipso-nitration reactions. Aromatic α,β-unsaturated carboxylic acids were smoothly converted to nitro-alkenes (69, 83-85) in up to 64 % yield (Scheme 5C; page S43).…”

Eine durch Elektronen angetriebene Nitrierung von Kohlenwasserstoffen

“…82 führt (Schema 5B). [42] Als Nächstes untersuchten wir die Möglichkeit der Einführung von Nitro-Gruppen über ipso-Nitrierungsreaktionen. Aromatische α,β-ungesättigte Carbonsäuren ließen sich problemlos in Nitroalkene (69, 83-85) in bis zu 64 % Ausbeute umwandeln (Schema 5C; Seite S43).…”

“…Wenn 4‐Phenylpent‐4‐ensäure oder 2‐(1‐Phenylvinyl)benzoesäure elektrochemischen Bedingungen ausgesetzt wurden, findet eine nitrative Lactonisierung statt, die zu γ‐Lactonen 81 bzw. 82 führt (Schema 5B) [42] . Als Nächstes untersuchten wir die Möglichkeit der Einführung von Nitro‐ Gruppen über ipso ‐Nitrierungsreaktionen.…”