Development of Tunable Single-Electron Transfer Reagents.

可调谐单电子转移试剂的开发。

• 批准号: 11672096
• 负责人: UCHIYAMA Masanobu
• 金额: $ 2.3万
• 依托单位: Tohoku University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 1999
• 资助国家: 日本
• 起止时间: 1999 至 2000
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-11672096/
• 关键词: ate complexes; single-electron transfer; desulfonylation; Me_3Mn(II)Li; Me_3Fe(II)Li; Me_3Co(II)Li; 鉄

The single-electron releasable ate complexes (hereafter denoted as "SER-ate complex"), i.e., lithium trimethylmanganate (Me_3Mn(II)Li), lithium trimethylferrate (Me_3Fe(II)Li), and lithium trimethylcobaltate (Me_3Co(II)Li) have been designed and clarified. We also discussed the essence and mechanism of their single-electron transfer (hereafter called SET) reaction using ab initio theoretical calculations, in situ (ATR)FTIR spectroscopy, and electrochemical methods. The results clearly reveal that these complexes are powerful and selective complex reagents for the SET reaction and can control their single-electron releasing ability to some extent by the ligation environment. Based on the obtained electrochemical information, we also developed the catalytic version of this SET system. This system turned out to be effective for the desulfonylation of all types of N-phenylsulfonyl amides, the chemoselective deprotection of the O-allyl/benzyl/tosyl/t-butyldimethylsilyl (TBDMS) groups, the reduction of the nitro groups, the partial reduction of the carbonyl groups of diketone, the reductive ligand coupling of the diphenyliodonium salt, and the reductive diaryl coupling of the dihalogen compounds via anion radical species with good to excellent yields under mild conditions. This system is a very attractive method for several reasons (simplicity, good availability, low cost, and easy operation) and would be particularly useful for large-scale reactions.

单电子可释放的Ate复合物（以下称为“ Ser-ate Complex综合体”），即三甲基甘烷酸锂（ME_3MN（II）LI），Trimethylferrate（Me_3fe（II）LI）和锂甲基甲基甲基甲基甲基（II）和三甲基甲基甲基甲基甲米甲基甲基甲酸锂（Me_3co（Me_3co）（II II）LI） ）已设计和澄清。我们还使用从头算理论计算，原位（ATR）FTIR光谱和电化学方法讨论了其单电子转移（以下称为SET）反应的本质和机制。结果清楚地表明，这些复合物是设定反应的功能强大且选择性的复杂试剂，并且可以通过连接环境在某种程度上控制其单电子释放能力。根据获得的电化学信息，我们还开发了此集合系统的催化版本。事实证明，该系统对于所有类型的N-苯基磺酰基酰胺，O-酰基/苯甲基/TOSYL/TOSYL/T-BUTYLDIMETHYLSILYL（TBDMS）组的化学选择性脱旋riptotion（TBDMS）组有效在二酮的羰基中，二苯基二元盐的还原性配体偶联以及在轻度条件下具有良好产量的二氢基因化合物的还原性日记偶联。由于几个原因（简单，良好的可用性，低成本和易于操作），该系统是一种非常有吸引力的方法，对于大规模反应特别有用。