ChemRxiv
These are preliminary reports that have not been peer-reviewed. They should not be regarded as conclusive, guide clinical practice/health-related behavior, or be reported in news media as established information. For more information, please see our FAQs.
ChemRxiv.pdf (632.72 kB)
0/0

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

preprint
submitted on 23.01.2020 and posted on 24.01.2020 by Daisuke Uraguchi, Fumito Ueoka, Naoya Tanaka, Tomohito Kizu, Wakana Takahashi, Takashi Ooi
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.

History

Email Address of Submitting Author

tooi@chembio.nagoya-u.ac.jp

Institution

Nagoya University

Country

Japan

ORCID For Submitting Author

0000-0003-2332-0472

Declaration of Conflict of Interest

No conflict of interest.

Exports