Structure and Reactivity Control of Ambiphilic Oxygen Species

两亲氧的结构和反应性控制

• 批准号: 03453092
• 负责人: SAWAKI Yasuhiko
• 金额: $ 5.06万
• 依托单位: Nagoya University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (B)
• 财政年份: 1991
• 资助国家: 日本
• 起止时间: 1991 至 1992
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-03453092/
• 关键词: Active oxygen species; Oxygenation; Singlet oxygen; Carbonyl oxide; Persulfoxide; Nitroso oxide; パースルオキシド; 酸素活性種

Structure and reactivity of XOO species as an important active oxygen species have been studies systematically. The characteristic reactivity of XOO species for carbonyl oxides (X = R_2C) and persulfoxides(X = R_2S) is a nucleophilic oxygen transfer to sulfoxides, which suggest that the XOO species are shown as a 1,3-dipolar reagent. In contrast, nitroso oxides (RNOO) transfer oxygen atoms as an electrophilic 1,3-diradical. The cyclization of XOO species to cyclic dioxiranes has been shown not to occur for the cases of carbonyl oxides and persulfoxides, which could be rationalized by the double bond nature of X-O bobd for X = C and S atoms. The cyclization of XOO species was shown to be facile for the case of nitroso oxides (X = N atoms), which reflects the single bond nature of N-O bond of RNOO 1,3-diradicals. The predominant factor controlling the reactivity of XOO species has been shown to be the electronegativity of X.

XOO物种作为一种重要的活性氧物种，其结构和反应活性已被系统地研究。XOO物种与羰基氧化物（X = R_2C）和全亚砜（X = R_2S）的反应特征是亲核氧转移到亚砜，表明XOO物种是一种1，3-偶极试剂。相反，亚硝基氧化物（RNOO）作为亲电1，3-双自由基转移氧原子。对于羰基氧化物和全亚砜的情况，XOO物种环化成环状二氧杂环丙烷已被证明是不发生的，这可以通过X = C和S原子的X-O bobd的双键性质来合理化。对于亚硝基氧化物（X = N原子），XOO物种的环化反应是容易的，这反映了RNOO 1，3-双自由基的N-O键的单键性质。控制XOO物种反应性的主要因素已被证明是X的电负性。

项目成果

K.Ishiguro,M.Ikeda,Y.Sawaki: "Formation of σ-Radical Cation Intermediates in the C-C Coupling Reaction of Phenyldiazomethanes by One-Electron Oxidation" J.Org.Chem.57. 3057-3066 (1992)

K. Ishiguro、M. Ikeda、Y. Sawaki：“通过单电子氧化在苯基重氮甲烷的 C-C 偶联反应中形成 σ-自由基阳离子中间体”J.Org.Chem.57 (1992)。

Y.Sugihara,Y.Watanabe,H.Kumura,T.Nakamura,S.Suyama,Y.Sawaki: "Radical Intermediates in the Thermal Decomposition of 1,1-Bis(t-bytyldioxy)cyclohexane" Bull.Chem.Soc.Jan.65. 664-667 (1992)

Y.Sugihara，Y.Watanabe，H.Kumura，T.Nakamura，S.Suyama，Y.Sawaki：“1,1-双（叔丁基二氧基）环己烷热分解中的自由基中间体”Bull.Chem.Soc。

S.Ishikawa,S.Tsuji,Y.Sawaki: "Structure and Reactivity of Nitroso Oxide" J.Am.Chem.Soc.113. 4282-4288 (1991)

S.Ishikawa、S.Tsuji、Y.Sawaki：“亚硝基氧化物的结构和反应性”J.Am.Chem.Soc.113。

K. Ishiguro, M. Ikeda, Y. Sawaki: "Formation of sigma-Radical Cation Intermediates in the C-C Coupling Reaction of Phenyldiazomethanes by One-Electron Oxidation" J. Org. Chem.57. 3057-3066 (1992)

K. Ishiguro、M. Ikeda、Y. Sawaki：“通过单电子氧化在苯基重氮甲烷的 C-C 偶联反应中形成 σ 自由基阳离子中间体”J. Org。

S.Ishikawa,S.Tsuji,Y.Sawaki: "Structure and Reactivity of Niroso Oxides" J.Amer.Chem.Soc.113. 4282-4288 (1991)

S.Ishikawa、S.Tsuji、Y.Sawaki：“亚硝基氧化物的结构和反应性”J.Amer.Chem.Soc.113。