期刊
CHEMISTRY-A EUROPEAN JOURNAL
卷 28, 期 37, 页码 -出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.202200932
关键词
Berry pseudorotation; continuous flow; nucleophilic substitution; phosphorus; phosphotriester
资金
- Tokyo Tech Challenging Research Award
- JSPS [19J14624, 18H04392, 21H01929]
- Sasakawa Scientific Research Grant [2021-3037]
- Grants-in-Aid for Scientific Research [19J14624, 18H04392, 21H01929] Funding Source: KAKEN
In this study, a sequential nucleophilic substitution reaction was demonstrated in a continuous-flow reactor, where the occurrence of over nucleophilic substitution during the reaction was suppressed by the addition of imidazole. The findings suggest that the presence of imidazole significantly improves the selectivity of the reaction.
We demonstrate a sequential nucleophilic substitution of highly electrophilic and inexpensive phosphorus trichloride with three different alcohols in a continuous-flow reactor. A variety of alcohols including ones that contained acid- and/or basic-labile functionalities were rapidly reacted. A over nucleophilic substitution that occurred during reaction of the second alcohol was suppressed by the addition of imidazole. Density functional theory calculations of the sequential nucleophilic substitutions of alcohols were performed both with and without imidazole, and Berry pseudorotation was suggested as a rate-limiting step in both cases. Herein, we discuss the reasons for the decreased selectivity in the absence of imidazole as well as those for improved selectivity in the presence of imidazole during the second nucleophilic substitution.
作者
我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。
推荐
暂无数据