Transforming Oxadiazolines through Nitrene Intermediates by Energy Transfer Catalysis: Access to Sulfoximines and Benzimidazoles

Park, Do Dam; Min, Kwan Hong; Kang, Jihee; Hwang, Ho Seong; Soni, Vineet Kumar; Cho, Cheon Gyu; Cho, Eun Jin

doi:10.1021/acs.orglett.9b04646

Cited by 15 publications

(13 citation statements)

References 56 publications

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“…Previously, the radical reaction of A ( E T = 55 kcal/mol) has been achieved by selective energy transfer with fac -Ir(ppy) 3 ( E T = 61 kcal/mol). The N–O homolysis of A generated a nitrene intermediate that was converted into benzimidazole by an intramolecular aromatic substitution process or to sulfoximine by coupling with sulfoxide . Remarkably, in the presence of O 2 , singlet oxygen generated by dual energy transfer participated in N–O bond homolysis to afford the iminyl radical intermediate, eventually leading to the synthesis of spiro-azalactam compounds …”

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confidence: 99%

Complementary Reactivity in Selective Radical Processes: Electrochemistry of Oxadiazolines to Quinazolinones

Hwang

Cho

2021

Org. Lett.

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Electrochemistry has recently emerged as a sustainable approach for efficiently generating radical intermediates utilizing eco-friendly electric energy. An electrochemical process was developed to transform 1,2,4-oxadiazolines under mild conditions. The electrochemical N−O bond cleavage at a controlled oxidation potential led to the selective synthesis of quinazolinone derivatives that could not be obtained by photocatalytic radical processes, indicating complementary reactivities in radical processes. The electrochemical reaction pathways were fully revealed by density functional theory-based investigations.

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confidence: 99%

Complementary Reactivity in Selective Radical Processes: Electrochemistry of Oxadiazolines to Quinazolinones

Hwang

Cho

2021

Org. Lett.

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“…Recent advances in visible-light photocatalysis, mediated by visible-lightabsorbing photosensitizers, have allowed ready access to complex molecules in a controlled manner, where subtle differences in the reaction conditions opened up distinct reaction pathways. [1][2][3][4][5] Imines are versatile substrates that can be converted into various azo-compounds, depending upon the reaction conditions. [6][7][8][9] In particular, the reactivities of Nbenzylidenes have been extensively explored under visible-light photocatalysis.…”

Section: Introductionmentioning

confidence: 99%

Distinctive Reactivity of N-benzylidene-[1,1'-biphenyl]-2-amines under Photoredox Catalysis

Tambe¹,

Min²,

Iqbal³

et al. 2020

Preprint

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A simple photocatalytic method was developed for the synthesis of unsymmetrical 1,2-diamines by the unprecedented reductive coupling of N-benzylidene-[1,1'-biphenyl]-2-amines with an aliphatic amine. The presence of phenyl substituent in the aniline moiety of the substrate was critical for the reactivity. The reaction proceeded via radical-radical cross-coupling of a-amino radicals generated by proton-coupled single-electron transfer in the presence of an Ir-photocatalyst. On the other hand, symmetrical 1,2-diamines were selectively produced from the same starting materials by judicious choice of the reaction conditions, showcasing the distinct reactivity of N-benzylidene-[1,1'-biphenyl]-2-amines. The developed method can be employed for the synthesis of various bulky vicinal diamines, which are potential ligands in stereoselective synthesis.

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“…The selective formation of distinct valuable compounds from the same starting material is a highly attractive divergent approach, though it represents significant synthetic challenges. Recent advances in visible-light photocatalysis, mediated by visible-light-absorbing photosensitizers, have allowed ready access to complex molecules in a controlled manner, where subtle differences in the reaction conditions opened up distinct reaction pathways [1][2][3][4][5].…”

Section: Introductionmentioning

confidence: 99%

Distinctive reactivity of N-benzylidene-[1,1'-biphenyl]-2-amines under photoredox conditions

Tambe

Min

Iqbal

et al. 2020

Beilstein J. Org. Chem.

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A simple photocatalytic method was developed for the synthesis of unsymmetrical 1,2-diamines by the unprecedented reductive coupling of N-benzylidene-[1,1'-biphenyl]-2-amines with an aliphatic amine. The presence of a phenyl substituent in the aniline moiety of the substrate was critical for the reactivity. The reaction proceeded via radical–radical cross-coupling of α-amino radicals generated by proton-coupled single-electron transfer in the presence of an Ir photocatalyst. On the other hand, symmetrical 1,2-diamines were selectively produced from the same starting materials by the judicious choice of the reaction conditions, showcasing the distinct reactivity of N-benzylidene-[1,1'-biphenyl]-2-amines. The developed method can be employed for the synthesis of various bulky vicinal diamines, which are potential ligands in stereoselective synthesis.

show abstract

Transforming Oxadiazolines through Nitrene Intermediates by Energy Transfer Catalysis: Access to Sulfoximines and Benzimidazoles

Cited by 15 publications

References 56 publications

Complementary Reactivity in Selective Radical Processes: Electrochemistry of Oxadiazolines to Quinazolinones

Complementary Reactivity in Selective Radical Processes: Electrochemistry of Oxadiazolines to Quinazolinones

Distinctive Reactivity of N-benzylidene-[1,1'-biphenyl]-2-amines under Photoredox Catalysis

Distinctive reactivity of N-benzylidene-[1,1'-biphenyl]-2-amines under photoredox conditions

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