A Structurally Robust Chiral Borate Ion: Molecular Design, Synthesis, and Asymmetric Catalysis

被引：0

作者：

Uraguchi, Daisuke ^{[1
]}

Ueoka, Fumito ^{[1
]}

Tanaka, Naoya ^{[1
]}

Kizu, Tomohito ^{[1
]}

Takahashi, Wakana ^{[1
]}

Ooi, Takashi ^{[1
,2
]}

机构：

[1] Department of Molecular and Macromolecular Chemistry, Graduate School of Engineering, Nagoya University, Nagoya,464-8603, Japan

[2] Institute of Transformative Bio-Molecules (WPI-ITbM), Nagoya University, Nagoya,464-8601, Japan

来源：

Advanced Materials | 2020年 / 132卷 / 28期

基金：

日本学术振兴会;

关键词：

Catalysis; -; Ions; Stereochemistry;

D O I：

10.1002/ANGE.202001637

中图分类号：

学科分类号：

摘要：

Catalysis by chiral weakly-coordinating anions (WCAs) remains underdeveloped due to the lack of a molecular design strategy for exploiting their characteristics, such as the non-nucleophilic nature. Here, we report the development of a chiral borate ion comprising an O,N,N,O-tetradentate backbone, which ensures hitherto unattainable structural robustness. Upon pairing with a proton, the hydrogen borate acts as an effective catalyst for the asymmetric Prins-type cyclization of vinyl ethers, providing access to structurally and stereochemically defined dihydropyrans. The key to selectivity control is the distinct ability of the borate ion to discriminate the prochiral faces of the acyclic oxonium ion intermediate and dictate the regiochemical outcome. We anticipate that this study paves the way for exploring the untapped potential of WCA catalysis for selective chemical synthesis. © 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

引用

页码：11553 / 11558