Synthesis of Visible-Light–Activated Hypervalent Iodine and Photo-oxidation under Visible Light Irradiation &lt;i&gt;via&lt;/i&gt; a Direct S&lt;sub&gt;0&lt;/sub&gt;→T&lt;sub&gt;n&lt;/sub&gt; Transition

Nakajima, Masaya; Nagasawa, Sho; Matsumoto, Koki; Matsuda, Yu; Nemoto, Tetsuhiro

doi:10.1248/cpb.c21-00899

Cited by 3 publications

(1 citation statement)

References 33 publications

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“…In 2020, Nakajima and Nemoto established that photoinduced reactions of heavy-atom-containing molecules, such as hypervalent iodine or bismuth compounds, proceed via direct S 0 –T n transition, with the aid of the relaxation of spin restrictions based on the internal heavy-atom effect (Fig. 1b-(I) ) 31 , 32 . Subsequently, in 2022, Mita and Maeda also featured the homolysis of P–P bonds via light absorption through direct S 0 –T n transition (Fig.…”

Section: Introductionmentioning

confidence: 99%

Vibration-mediated long-wavelength photolysis of electronegative bonds beyond S0–S1 and S0–T1 transitions

Araujo Dias,

Muranaka,

Uchiyama

et al. 2024

Commun Chem

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Photolysis is an attractive method in organic synthesis to produce free radicals through direct bond cleavage. However, in this method, specific irradiation wavelengths of light have been considered indispensable for excitation through S0–Sn or S0–Tn transitions. Here we report the photoinduced homolysis of electronegative interelement bonds using light at wavelengths much longer than theoretically and spectroscopically predicted for the S0–Sn or S0–Tn transitions. This long-wavelength photolysis proceeds in N–Cl, N–F, and O–Cl bonds at room temperature under blue, green, and red LED irradiation, initiating diverse radical reactions. Through experimental, spectroscopic, and computational studies, we propose that this “hidden” absorption is accessible via electronic excitations from naturally occurring vibrationally excited ground states to unbonded excited states and is due to the electron-pair repulsion between electronegative atoms.

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Section: Introductionmentioning

confidence: 99%

Vibration-mediated long-wavelength photolysis of electronegative bonds beyond S0–S1 and S0–T1 transitions

Araujo Dias,

Muranaka,

Uchiyama

et al. 2024

Commun Chem

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Triplet Energy Transfer Mechanism in Copper Photocatalytic N‐ and O‐Methylation

Hoving,

Haaksma,

Stoppel

et al. 2024

Chemistry A European J

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Methylation reactions are chemically simple but challenging to perform under mild and non‐toxic conditions. A photochemical energy transfer strategy was merged with copper catalysis to enable fast reaction times of minutes and broad applicability to N‐heterocycles, (hetero‐)aromatic carboxylic acids, and drug‐like molecules in high yields and good functional group tolerance. Detailed mechanistic investigations, using kinetic analysis, aprotic MS, UV/Vis, and luminescence quenching experiments revealed a triplet‐triplet energy transfer mechanism between hypervalent iodine(III) reagents and readily available photosensitizers.

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Direct S₀ → T_n Transition under Visible Light Irradiation Enabling Synthesis of a Pseudoindoxyl Scaffold

Nakajima,

Nagasawa,

Yamazaki

et al. 2024

Org. Lett.

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Pseudoindoxyl is a partial skeleton found in various natural products. Its light-absorption properties make it useful for the design of functional molecules. However, versatile synthesis methods have not yet been reported. In this report, we present a versatile synthetic method for pseudoindoxyls using the direct S0 → Tn transition under visible light irradiation. We also discuss the application of pseudoindoxyls as photocatalysts.

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Synthesis of Visible-Light–Activated Hypervalent Iodine and Photo-oxidation under Visible Light Irradiation <i>via</i> a Direct S<sub>0</sub>→T<sub>n</sub> Transition

Cited by 3 publications

References 33 publications

Vibration-mediated long-wavelength photolysis of electronegative bonds beyond S0–S1 and S0–T1 transitions

Vibration-mediated long-wavelength photolysis of electronegative bonds beyond S0–S1 and S0–T1 transitions

Triplet Energy Transfer Mechanism in Copper Photocatalytic N‐ and O‐Methylation

Direct S₀ → T_n Transition under Visible Light Irradiation Enabling Synthesis of a Pseudoindoxyl Scaffold

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Synthesis of Visible-Light–Activated Hypervalent Iodine and Photo-oxidation under Visible Light Irradiation <i>via</i> a Direct S<sub>0</sub>→T<sub>n</sub> Transition

Cited by 3 publications

References 33 publications

Vibration-mediated long-wavelength photolysis of electronegative bonds beyond S0–S1 and S0–T1 transitions

Vibration-mediated long-wavelength photolysis of electronegative bonds beyond S0–S1 and S0–T1 transitions

Triplet Energy Transfer Mechanism in Copper Photocatalytic N‐ and O‐Methylation

Direct S0 → Tn Transition under Visible Light Irradiation Enabling Synthesis of a Pseudoindoxyl Scaffold

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Direct S₀ → T_n Transition under Visible Light Irradiation Enabling Synthesis of a Pseudoindoxyl Scaffold