Cerium(IV) ammonium nitrate: Reagent for the versatile oxidative functionalization of styrenes using N-hydroxyphthalimide

Krylov, Igor B.; Paveliev, Stanislav A.; Matveeva, Olesya K.; Terent’ev, Alexander O.

doi:10.1016/j.tet.2019.03.030

Cited by 23 publications

(9 citation statements)

References 47 publications

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“…56 However, we should note that the free radical diazidation of the acrylate moiety was reported previously 28 as well as the addition of electrophilic PINO radicals to methyl methacrylate. 7,57 To confirm the regioselectivity of the addition of azide and N-oxyl radicals, we performed X-ray diffraction analysis for product 3ja (Scheme 3). Regioselectivity was also confirmed by two-dimensional 1 H− 15 N HMBC and 14 N and 1 H− 13 C HMBC spectra (see the Supporting Information).…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Free Radicals in the Queue: Selective Successive Addition of Azide and N-Oxyl Radicals to Alkenes

Lopat’eva,

Krylov,

Paveliev

et al. 2023

J. Org. Chem.

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The selective successive addition of azide (•N3) and N-oxyl radicals to alkenes is demonstrated, despite each of the two radicals being known to attack CC bonds and the mixture of radical adducts possibly being expected. The proposed radical mechanism was supported by density functional theory calculations, electron paramagnetic resonance, and radical trapping experiments. The reaction proceeds at room temperature with the available reagents: NaN3, N-hydroxy compounds, and PhI(OAc)2 as the oxidant. The method can be applied for N-hydroxyimides, N-hydroxyamides, N-hydroxybenzotriazole, and oximes as N-oxyl radical precursors. Vinylarenes, aliphatic alkenes, and even electron-deficient methyl methacrylate were successfully functionalized.

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Section: ■ Results and Discussionmentioning

confidence: 99%

Free Radicals in the Queue: Selective Successive Addition of Azide and N-Oxyl Radicals to Alkenes

Lopat’eva,

Krylov,

Paveliev

et al. 2023

J. Org. Chem.

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“…However, no obvious enhancement in the activity was observed at Ce(SO 4 ) 2 /RuTPP = 4, but the selectivity sharply declined. As the amount of Ce(SO 4 ) 2 increased, the yield of acrolein and other products increased, which indicates Ce(SO 4 ) 2 promotes the generation of allyl free radicals via the deprotonation at the α-carbon of propylene. − …”

Section: Resultsmentioning

confidence: 99%

Cerium(IV) Sulfate as a Cocatalyst for Promoting the Direct Epoxidation of Propylene by Ruthenium Porphyrin with Molecular Oxygen

Zhou

et al. 2020

Ind. Eng. Chem. Res.

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The direct epoxidation of propylene to propylene oxide (PO) using molecular oxygen is difficult to achieve. Liquid-phase aerobic propylene epoxidation has been achieved using metalloporphyrin catalysts, but the efficiency was poor. Herein, the direct aerobic epoxidation of propylene was accomplished using ruthenium porphyrin with Ce(SO 4 ) 2 as a cocatalyst. The propylene conversion and PO selectivity were 33.7% and 82.3%, respectively. The efficiency was approximately 2 times higher than RuTPP (ruthenium mesotetraphenylporphyrin) alone and more than 3 times higher than Ce(SO 4 ) 2 alone. Ce(IV) promoted the formation of allyl radicals and promoted the oxidative cleavage of the CC bond of propylene.

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“…[13] Generation of imide-N-oxyl radicals as a result of anodic oxidation of N-hydroxyimides and their selective reactions with substrates remains problematic due to the low stability of such radicals under electrochemical conditions and their tendency to self-decomposition. [14] Although imide-Noxyl radicals are widespread in many processes of CÀ O coupling [15] and functionalization of alkenes, [16] their use in electroorganic synthesis is limited to reactions in which they act as mediators of benzylic [17] and allylic [18] CÀ H functionalization, as well as various oxidation processes. [19] Reactions involving vinyl azides, in which various radical species add to the terminal carbon atom of the double C=C bond of vinyl azide with the release of N 2 molecule, gain growing interest (Scheme 1).…”

Section: Introductionmentioning

confidence: 99%

Electrochemical Synthesis of O‐Phthalimide Oximes from α‐Azido Styrenes via Radical Sequence: Generation, Addition and Recombination of Imide‐N‐Oxyl and Iminyl Radicals with C−O/N−O Bonds Formation

et al. 2020

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Electrochemically induced radical‐initiated reaction of vinyl azides with N‐hydroxyphthalimide resulting O‐phthalimide oximes with challenging for organic chemistry N−O‐N fragment has been discovered. The developed approach introduces in synthesis electrochemically generated O‐centered imide‐N‐oxyl radicals as the coupling components. Sequential formation of C−O and N−O bonds was achieved via generation and selective addition of imide‐N‐oxyl radicals, followed by recombination with iminyl radicals. A wide range of O‐phthalimide oximes was obtained with the yields up to 84%.

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Cerium(IV) ammonium nitrate: Reagent for the versatile oxidative functionalization of styrenes using N-hydroxyphthalimide

Cited by 23 publications

References 47 publications

Free Radicals in the Queue: Selective Successive Addition of Azide and N-Oxyl Radicals to Alkenes

Free Radicals in the Queue: Selective Successive Addition of Azide and N-Oxyl Radicals to Alkenes

Cerium(IV) Sulfate as a Cocatalyst for Promoting the Direct Epoxidation of Propylene by Ruthenium Porphyrin with Molecular Oxygen

Electrochemical Synthesis of O‐Phthalimide Oximes from α‐Azido Styrenes via Radical Sequence: Generation, Addition and Recombination of Imide‐N‐Oxyl and Iminyl Radicals with C−O/N−O Bonds Formation

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