<i>N</i>-Heterocyclic Carbene Nitric Oxide Radicals

Park, Junbeom; Song, Hayoung; Kim, Young-Suk; Eun, Bit; Kim, Yonghwi; Bae, Dae Young; Park, Sungho; Rhee, Young Min; Kim, Won Jong; Kim, Kimoon; Lee, Eunsung

doi:10.1021/jacs.5b01976

Cited by 43 publications

(41 citation statements)

References 39 publications

(12 reference statements)

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“…However,r eaction of 1 with neither triflic acid (HOTf) nor lutidinium triflate (LutHOTf) afforded 5,a st he products from both reactions exhibited no EPR signal. Instead of the radical cation 5,t he reaction between 1 and astoichiometric amount of LutHOTf resulted in a1:1 mixture of two non-radical products: ( 7). It is notable that this reactivity resembles the disproportionation of aminoxyl radicals triggered by strong acids.…”

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confidence: 99%

“…[6] Recently,our group reported the synthesis and characterization of the stable N-heterocyclic carbene stabilized nitric oxide radicals (NHCNOs). [7] Interestingly,NHCNO (1)reacts with trimethylsilyl triflate (TMSOTf) and triisopropylsilyl triflate (TIPSOTf)t og enerate the radical cations 2a or 2b, respectively (Scheme 2). This reactivity resembles the addition of various reagents to N-heterocyclic carbene nitrous oxides (NHCN 2 O), reactivity which was intensively studied by the group of Severin.…”

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Oxime Ether Radical Cations Stabilized by N‐Heterocyclic Carbenes

Kim

Lee

2017

Angew Chem Int Ed

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N-heterocyclic carbene (NHC) nitric oxide (NHCNO) radicals,w hichc an be regarded as iminoxyl radicals stabilized by NHCs,w ere found to react with as eries of silyl and alkyltriflates to generate the corresponding oxime ether radical cations.The structures of the resulting oxime ether radical cations were determined by X-rayc rystallography, along with EPR and computational analysis.I nc ontrast, lutidinium triflate produced a1 :1 mixture of [u pon the reaction with NHCNO.T his study adds an important example of stable singlet carbenes for stabilizing main-group radicals because of their p-conjugating effect, the synthesis and structures of which have not been reported previously.

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Oxime Ether Radical Cations Stabilized by N‐Heterocyclic Carbenes

Kim

Lee

2017

Angew Chem Int Ed

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“…In 2015, our group reportedt he first synthesis of NHC-derived nitroxyl radicals 64 and 65 from the reaction of NHCs with nitric oxide (NO) (Scheme16). [62] The radicals are stable enough to be characterized by X-ray crystallography and EPR spectroscopy.T he SOMOs of the resulting iminoxyl radicals are delocalized over the imidazole ring and nitric oxide moiety.…”

Section: Nitroxyl Radicalsmentioning

confidence: 99%

Stable Organic Radicals Derived from N‐Heterocyclic Carbenes

Kim

Lee

2018

Chemistry A European J

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Over the past decade, numerous stable organic and main-group radicals have been synthesized from N-heterocyclic carbenes (NHCs). The structure of NHCs, in particular, offers electronic stabilization that helps to delocalize the unpaired electron over the molecule. In addition, the sterically bulky substituents of NHCs protect the radical center to prevent detrimental reactions such as dimerization. These advantages enable the straightforward synthesis and characterization of various interesting organic radicals starting from NHCs, which are, these days, widely available. NHCs have enabled the structural characterization of various organic radicals over the past decade, including α-carbonyl, propargyl, oxyallyl, and triazenyl radicals as notable examples. This minireview summarizes the advances in this field, mainly focusing on the preparation and stability as well as the properties and applications of NHC-derived organic radicals.

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“…374 Thermal decomposition of the radical leads to imidazolones of the type 98C and the initial carbene 98A. 4.4.8.…”

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confidence: 99%