Direct oxidative installation of nitrooxy group at benzylic positions and its transformation into various functionalities

Aerobic oxidation of secondary alcohols using NHPI and iron salt as catalysts at room temperature

“…Therefore, oxygen as clean oxidant for the selective oxidation of alcohols to carbonyl compounds under mild conditions is more attractive since the main by-product is water [14][15][16]. And NHPI is recognized as one of powerful catalysts for aerobic oxidation of various organic compounds [17][18][19][20][21][22].…”

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.…”

“…The requirement for prefunctionalized starting materials presents as ynthetic limitation in all cases,w hile further drawbacks include the moisture sensitivity and thermal instability of reagents,the use of strong oxidants,aswell as harsh reaction conditions and poor functional group tolerance.A lternative strategies include the oxidative nitration of alkenes using tertbutyl nitrite/O 2 , [17] CANi nt he presence and absence of nucleophilic partners, [18] and Hg II salts with halogens, [19] but adrawback to these examples remains the need for hazardous reagents,a swell as the formation of product mixtures or dinitrooxylated products.F urther methodologies include aC AN-mediated radical alkylation, which although interesting from amechanistic standpoint, presents limited synthetic applicability and scope. [20] More recently,aCAN-mediated benzylic nitrooxylation, [21] and the formal insertion of HNO 3 into aryldiazoacetates [22] have been described.…”

A highly site-selective radical sp3 C–H amination of azaheterocycles

“…We further believed that site selectivity could be additionally enhanced by including (and optimizing) an organic hydrogen atom transfer (HAT) catalyst. 11 We recently demonstrated that iron tris(pyrazole)borate catalysts could be used to direct methylene oxidation towards heterobenzylic positions in combination with an organic HAT catalyst. 12 …”