Selective monodeuteration enabled by bisphosphonium catalyzed ring opening processes

IF 14.7 1区 综合性期刊 Q1 MULTIDISCIPLINARY SCIENCES
Yuanli Xu, Wenlong Chen, Ruihua Pu, Jia Ding, Qing An, Yi Yang, Weimin Liu, Zhiwei Zuo
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引用次数: 0

Abstract

The selective incorporation of a deuterium atom into small molecules with high selectivity is highly valuable for medical and chemical research. Unfortunately, this remains challenging due to the complete deuteration caused by commonly used hydrogen isotope exchange strategies. We report the development of a photocatalytic selective monodeuteration protocol utilizing C–C bond as the unconventional functional handle. The synergistic combination of radical-mediated C–C bond scission and deuterium atom transfer processes enables the effective constructions of benzylic CDH moieties with high selectivity for monodeuteration. The combinational use of a bisphosphonium photocatalyst, thiol catalyst, and CH3OD deuteration agent provides operationally simple conditions for photocatalytic monodeuteration. Moreover, the photoinduced electron transfer process of the bisphosphonium photocatalyst is elucidated through a series of spectroscopy experiments, identifying a peculiar back electron transfer process that can be regulated by subsequent nucleophilic additions.

Abstract Image

通过双膦催化的开环过程实现选择性单脱氢
高选择性地在小分子中加入一个氘原子对医学和化学研究非常有价值。遗憾的是,由于常用的氢同位素交换策略会导致完全氘化,这仍然具有挑战性。我们报告了利用 C-C 键作为非常规官能团的光催化选择性单氘化协议的开发情况。将自由基介导的 C-C 键断裂和氘原子转移过程协同结合起来,可以有效地构建出具有高选择性的苄基 CDH 单氘化分子。双膦光催化剂、硫醇催化剂和 CH3OD 氚化剂的组合使用为光催化单氚化提供了操作简单的条件。此外,还通过一系列光谱实验阐明了双膦光催化剂的光诱导电子转移过程,确定了一个特殊的反向电子转移过程,该过程可通过后续的亲核添加进行调节。
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来源期刊
Nature Communications
Nature Communications Biological Science Disciplines-
CiteScore
24.90
自引率
2.40%
发文量
6928
审稿时长
3.7 months
期刊介绍: Nature Communications, an open-access journal, publishes high-quality research spanning all areas of the natural sciences. Papers featured in the journal showcase significant advances relevant to specialists in each respective field. With a 2-year impact factor of 16.6 (2022) and a median time of 8 days from submission to the first editorial decision, Nature Communications is committed to rapid dissemination of research findings. As a multidisciplinary journal, it welcomes contributions from biological, health, physical, chemical, Earth, social, mathematical, applied, and engineering sciences, aiming to highlight important breakthroughs within each domain.
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