Synthesis of Aminoboronic Acid Derivatives from Amines and Amphoteric Boryl Carbonyl Compounds

• Published in: Angewandte Chemie International Edition 2016-10, Vol.55 (41), p.12659-12663
• Main Authors: Diaz, Diego B., Scully, Conor C. G., Liew, Sean K., Adachi, Shinya, Trinchera, Piera, St. Denis, Jeffrey D., Yudin, Andrei K.
• Format: Article
• Language: English
• Subjects: Acids; Aldehydes; Aldehydes - chemistry; Amines; Amines - chemistry; Amphoterics; Biocompatibility; Boron; Boronic Acids - chemical synthesis; Boronic Acids - chemistry; Carbonyl compounds; Carbonyls; Chemical reactions; Chemical synthesis; Coupling (molecular); Cross coupling; Derivatives; Fragments; Molecular Structure; NMR spectroscopy; Peptides; peptidomimetics; reaction kinetics; Stereoisomerism; tautomerism
• ISSN: 1433-7851; 1521-3773
• DOI: 10.1002/anie.201605754

Herein, we demonstrate the use of α‐boryl aldehydes and acyl boronates in the synthesis of aminoboronic acid derivatives. This work highlights the untapped potential of boron‐substituted iminium ions and offers insights into the behavior of N‐methyliminodiacetyl (MIDA) boronates during condensation and tautomerization processes. The preparative value of this contribution lies in the demonstration that various amines, including linear and cyclic peptides, can be readily conjugated with boron‐containing fragments. A mild deprotection of amino MIDA‐boronates enables access to α‐ and β‐aminoboronic acids in high chemical yields. This simple process should be applicable to the synthesis of a wide range of bioactive molecules as well as precursors for cross‐coupling reactions. α‐Boryl aldehydes and acyl boronates are used in the synthesis of the title compounds. Various amines, including linear and cyclic peptides, can be readily conjugated with boron‐containing fragments, and mild deprotection of amino MIDA‐boronates enables access to α‐ and β‐aminoboronic acids in high yields.