Saturated Boronic Acids, Boronates, and Trifluoroborates: An Update on Their Synthetic and Medicinal Chemistry

• Published in: Chemistry : a European journal 2021-11, Vol.27 (62), p.15277-15326
• Main Authors: Volochnyuk, Dmitriy M., Gorlova, Alina O., Grygorenko, Oleksandr O.
• Format: Article
• Language: English
• Subjects: boronation; cross-coupling; metalocatalysis; organoboron compounds; organocatalysis; photochemical reactions
• ISSN: 0947-6539; 1521-3765
• DOI: 10.1002/chem.202102108

This review discusses recent advances in the chemistry of saturated boronic acids, boronates, and trifluoroborates. Applications of the title compounds in the design of boron‐containing drugs are surveyed, with special emphasis on α‐amino boronic derivatives. A general overview of saturated boronic compounds as modern tools to construct C(sp3)−C and C(sp3)‐heteroatom bonds is given, including recent developments in the Suzuki‐Miyaura and Chan‐Lam cross‐couplings, single‐electron‐transfer processes including metallo‐ and organocatalytic photoredox reactions, and transformations of boron “ate” complexes. Finally, an attempt to summarize the current state of the art in the synthesis of saturated boronic acids, boronates, and trifluoroborates is made, with a brief mention of the “classical” methods (transmetallation of organolithium/magnesium reagents with boron species, anti‐Markovnikov hydroboration of alkenes, and the modification of alkenyl boron compounds) and a special focus on recent methodologies (boronation of alkyl (pseudo)halides, derivatives of carboxylic acids, alcohols, and primary amines, boronative C−H activation, novel approaches to alkene hydroboration, and 1,2‐metallate‐type rearrangements). Organoboron compounds. The chemistry of saturated boronic acids, boronates, and trifluoroborates is reviewed. Applications of the title compounds in the design of boron‐containing drugs and as tools to construct C(sp3)−C and C(sp3)‐heteroatom bonds are discussed. The current state of the art in the synthesis of saturated boronic derivatives is described, with a special focus on methodologies developed over the last decade.