Synthesis of Acylborons by Ozonolysis of Alkenylboronates: Preparation of an Enantioenriched Amino Acid Acylboronate

Jumpei Taguchi; Toshiki Ikeda; Rina Takahashi; Ikuo Sasaki; Yasushi Ogasawara; Tohru Dairi; Naoya Kato; Yasunori Yamamoto; Jeffrey W Bode; Hajime Ito

doi:10.1002/anie.201707933

Synthesis of Acylborons by Ozonolysis of Alkenylboronates: Preparation of an Enantioenriched Amino Acid Acylboronate

Angew Chem Int Ed Engl. 2017 Oct 23;56(44):13847-13851. doi: 10.1002/anie.201707933. Epub 2017 Sep 29.

Authors

Affiliations

¹ Division of Applied Chemistry and Frontier Chemistry Center, Faculty of Engineering, Hokkaido University, Kita 13 Nishi 8 Kita-ku, Sapporo, Hokkaido, 060-8628, Japan.
² Department of Chemistry and Biological Science, College of Science and Engineering, Aoyama Gakuin University, 5-10-1, Fuchinobe, Chuo-ku, Sagamihara-shi, 252-5258, Japan.
³ Laboratorium für Organische Chemie, Department of Chemistry and Applied Bioscience, ETH Zürich, 8093, Zürich, Switzerland.

PMID: 28905460
DOI: 10.1002/anie.201707933

Abstract

A concise synthesis of acylborons was achieved by ozonolysis of alkenyl MIDA (N-methyliminodiacetic acid) boronates. This reaction exhibits excellent functional-group tolerance and is applicable to various acyl MIDA boronates and potassium acyltrifluroborates (KATs) which could not be synthesized by previous methods. In addition, α-amino acylborons, which would be essential for peptide ligations, were prepared for the first time. The acylboron of l-alanine was obtained in high enantiopurity and found to be configurationally stable. Oligopeptide synthesis between the α-amino KATs and amino acid in dilute aqueous media was studied.

Keywords: amino acids; boron; chemical ligation; ozonolysis; peptides.

Publication types

Research Support, Non-U.S. Gov't