2‐Methoxyethyl Nitrite as a Reagent for Chemoselective On‐Water Nitration. Issue 16 (15th June 2022)

• Record Type: Journal Article
• Authors: Kitanosono, Taku; Hashidoko, Airu; Yamashita, Yasuhiro; Kobayashi, Shū
• Is Part Of: Chemistry, an Asian journal. Volume 17:Issue 16(2022)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2022-06-15
• Subjects: on-water -- radical reactions -- organic nitrite -- nitrogen oxides -- nitration -- interface; Chemistry -- Periodicals; 540.5
• DOI: 10.1002/asia.202200457
• Languages: English
• ISSNs: 1861-4728

Abstract

Abstract: An on‐water approach has been developed that allows a nitration of tyrosines and phenols under mild conditions. We envisioned that the assembly of tyrosine/tyrosyl radical couples with interfacial water molecules would realize a biomimetic stacking hydrogen atom transfer (HAT) transition state to facilitate the electron‐transfer process. The optimal organic nitrite, 2‐methoxyethyl nitrite, resulted in rapid coupling of the tyrosyl radicals with ⋅NO2 at the oil–water interface to afford the nitrated phenols. Many characteristics found in our on‐water strategy are distinct from other complementary systems that include radical nitration. These enticing roles of water in the reaction process introduce new avenues to explore in the design of synthetic organic chemistry systems. Abstract : An on‐water approach has been developed that allows a chemoselective nitration of tyrosines and phenols. The enticing roles of water in the reaction process introduce new avenues to explore in the design of synthetic organic chemistry systems.