LiO-t-Bu/CsF-Mediated Formal Hydrolysis of Trifluoromethyl Arenes

Masanori Shigeno; Moe Kiriyama; Koki Izumi; Keita Sasaki; Ozora Sasamoto; Kanako Nozawa-Kumada; Yoshinori Kondo

doi:10.1055/a-2236-0209

Synthesis, Table of Contents

Synthesis 2024; 56(09): 1438-1448
DOI: 10.1055/a-2236-0209

paper

LiO-t-Bu/CsF-Mediated Formal Hydrolysis of Trifluoromethyl Arenes

Authors

Masanori Shigeno∗

^aDepartment of Biophysical Chemistry, Graduate School of Pharmaceutical Science, Tohoku University, Aoba, Sendai, 980-8578, Japan

^bJST, PRESTO, Kawaguchi, Saitama 332-0012, Japan
Moe Kiriyama

^aDepartment of Biophysical Chemistry, Graduate School of Pharmaceutical Science, Tohoku University, Aoba, Sendai, 980-8578, Japan
Koki Izumi

^aDepartment of Biophysical Chemistry, Graduate School of Pharmaceutical Science, Tohoku University, Aoba, Sendai, 980-8578, Japan
Keita Sasaki

^aDepartment of Biophysical Chemistry, Graduate School of Pharmaceutical Science, Tohoku University, Aoba, Sendai, 980-8578, Japan
Ozora Sasamoto

^aDepartment of Biophysical Chemistry, Graduate School of Pharmaceutical Science, Tohoku University, Aoba, Sendai, 980-8578, Japan
Kanako Nozawa-Kumada

^aDepartment of Biophysical Chemistry, Graduate School of Pharmaceutical Science, Tohoku University, Aoba, Sendai, 980-8578, Japan

^cInterdisciplinary Research Center for Catalytic Chemistry, National Institute of Advanced Industrial Science and Technology (AIST), Central 5, 1-1-1 Higashi, Tsukuba 305-8565, Ibaraki, Japan
Yoshinori Kondo

^aDepartment of Biophysical Chemistry, Graduate School of Pharmaceutical Science, Tohoku University, Aoba, Sendai, 980-8578, Japan

Abstract

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Abstract

This study investigates the formal hydrolysis of trifluoromethyl arenes without deprotonation functionality utilizing a combined Brønsted base system comprising LiO-t-Bu and CsF. The reaction conditions were optimized using 4-(trifluoromethyl)biphenyl as the model substrate, achieving a 94% yield with LiO-t-Bu/CsF. The scope of the substrate was explored, demonstrating the applicability of the system to various functionalities, such as (hetero)aryl, tert-butyl, methyl, amide, and alkenyl moieties. Mechanistic insights suggest a single electron transfer process.

Key words

trifluoromethyl arene - hydrolysis - combined Brønsted base - single-electron transfer - aromatic carboxylic acid

Full Text

References

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