Development of a nucleophilic deuteration method by using heavy water without any transition metal

开发使用重水且不含任何过渡金属的亲核氘化方法

• 批准号: 23655030
• 负责人: KANO Naokazu
• 金额: $ 2.33万
• 依托单位: The University of Tokyo
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Challenging Exploratory Research
• 财政年份: 2011
• 资助国家: 日本
• 起止时间: 2011 至 2012
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-23655030/
• 关键词: リン; 同位体標識; 重水; 重水素化; 超原子価; 極性変換; 還元; ヒドリド還元; 超原子価化合物

Deuteride reduction reactions of carbonyl compounds were developed by using the umpolung of heavy water under mild conditions without the presence of a transition metal. Ate-type hexacoordinated phosphorus compounds bearing two P-H bonds were synthesized as stable compounds. Two isomers around the phosphorus atom were isolated. Both isomers showed H-D exchange reactivity toward heavy water and hydride reduction reactivity toward carbonyl compounds. The reactivities of one isomer differ from those of the other isomer. Reaction conditions for the one-pot reaction of these two reactions were found, and the carbonyl compounds were formally reduced with heavy water. Therefore, a nucleophilic reductive deuteration method by using heavy water were successfully developed.

在无过渡金属存在的温和条件下，利用重水的质子化作用，发展了羰基化合物的氘还原反应。合成了稳定的含两个P-H键的六配位磷化合物。分离出磷原子周围的两种异构体。两种异构体都表现出对重水的H-D交换反应性和对羰基化合物的氢化物还原反应性。一种异构体的反应性不同于另一种异构体。找到了这两个反应的一锅反应条件，并用重水对羰基化合物进行了形式还原。因此，成功地发展了重水亲核还原氘代反应方法。

项目成果

Isolation of a Metastable Geometrical Isomer of a Hexacoordinated Dihydrophosphate : Elucidation of Its Enhanced Reactivity in Umpolung of a Hydrogen Atom of Wate

六配位二氢磷酸亚稳态几何异构体的分离：阐明其在水氢原子的反极性中增强的反应性

• DOI: 10.1021/ic2012765
• 发表时间: 2011
• 期刊: Inorganic Chemistry
• 影响因子: 4.6
• 作者: Hideaki Miyake;Naokazu Kano;Takayuki Kawashima
• 通讯作者: Takayuki Kawashima

Reductive deuteration of carbonyl compounds with deuterium oxide by using hexacoordinated dihydrophosphates

使用六配位二氢磷酸盐用氧化氘还原羰基化合物

• 发表时间: 2012
• 作者: Naokazu Kano;Hideaki Miyake;Takayuki Kawashima
• 通讯作者: Takayuki Kawashima