Synthesis of Aminoboronic Acids and Their Applications in Bifunctional Catalysis
- 16 April 2009
- journal article
- research article
- Published by American Chemical Society (ACS) in Accounts of Chemical Research
- Vol. 42 (6), 756-768
- https://doi.org/10.1021/ar800262v
Abstract
Amino acids have been known to catalyze organic reactions for many years, but their boronic acid counterparts are much less well-studied. Although there are a number of useful general approaches to the synthesis of protected aminoboronic acids, many practical challenges remain in the isolation and purification of free aminoboronic acids. Despite these issues, now several different chiral and achiral aminoboronic acids show promise as bifunctional organic catalysts. In this Account, we describe both advances in the synthesis of these aminoboronic acids and some of their underdeveloped potential in catalysis. The first aminoboronic acids that demonstrated catalytic properties, such as 8-quinoline boronic acid, enabled the hydrolysis and etherification of chlorohydrins. More recently, aminoboronic acids have effectively catalyzed direct amide formation. In addition, these catalysts can enable the kinetic resolution of racemic amines during the acylation process. Aminoboronic acids can also function as aldol catalysts, acting through in situ boronate enolate formation in water, and have facilitated tunable asymmetric aldol reactions, acting through the formation of an enamine. On the basis of these examples, we expect that these molecules can catalyze an even wider range of reactions. We anticipate many further discoveries in this area.Keywords
This publication has 47 references indexed in Scilit:
- A (−)-Sparteine-Directed Highly Enantioselective Synthesis of Boroproline. Solid- and Solution-State Structure and PropertiesThe Journal of Organic Chemistry, 2007
- Synthesis and Structure of Planar Chiral, Bifunctional Aminoboronic Acid Ferrocene DerivativesOrganometallics, 2007
- Synthesis and structure of bifunctional N-alkylbenzimidazole phenylboronate derivativesOrganic & Biomolecular Chemistry, 2006
- Mechanically Induced Expeditious and Selective Preparation of Disubstituted Pyridine/Pyrimidine Ferrocenyl ComplexesOrganometallics, 2004
- .alpha.-Halo boronic esters: intermediates for stereodirected synthesisChemical Reviews, 1989
- Stereoselective synthesis. VIII. Absolute configuration of a 1,2-disubstituted ferrocene derivative with planar and central elements of chirality and the mechanism of the optically active .alpha.-ferrocenyl tertiary aminesJournal of the American Chemical Society, 1973
- Organoboron Compounds. XVI. Coöperative Functional Group Effects in Reactions of BoronoarylbenzimidazolesJournal of the American Chemical Society, 1963
- Organoboron Compounds. XV.1 Stereochemistry of the Reaction of 8-Quinolineboronic Acid with ChloroalcoholsJournal of the American Chemical Society, 1963
- Organoboron Compounds. XIV.1,2 Polyfunctional Catalysis by 8-Quinolineboronic AcidJournal of the American Chemical Society, 1963
- Organoboron Compounds. IX. 8-Quinolineboronic Acid, its Preparation and Influence on Reactions of Chlorohydrins1Journal of the American Chemical Society, 1959