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Review
. 2024 Feb 16;89(4):2069-2089.
doi: 10.1021/acs.joc.2c01695. Epub 2022 Nov 14.

Emergent Organoboron Acid Catalysts

Brian J Graham  1 , Ronald T Raines  1
Affiliations
Review

Emergent Organoboron Acid Catalysts

Brian J Graham et al. J Org Chem. .

Abstract

Organoboron acids are stable, organic-soluble Lewis acids with potential application as catalysts for a wide variety of chemical reactions. In this review, we summarize the utility of boronic and borinic acids, as well as boric acid, as catalysts for organic transformations. Typically, the catalytic processes exploit the Lewis acidity of trivalent boron, enabling the reversible formation of a covalent bond with oxygen. Our focus is on recent developments in the catalysis of dehydration, carbonyl condensation, acylation, alkylation, and cycloaddition reactions. We conclude that organoboron acids have a highly favorable prospectus as the source of new catalysts.

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Figure 1.
Figure 1.
Structures of the various oxidation states of organoboron derivatives. R1, R2, R3 = alkyl, aryl, vinyl, alkynyl.
Figure 2.
Figure 2.
Representative reactions that are catalyzed by organoboron acids: dehydration, carbonyl condensation, acylation, alkylation, and cycloaddition. R1, R2 = alkyl, aryl, vinyl, alkynyl, hydroxy.
Figure 3.
Figure 3.
Key intermediates proposed by (A) Ishihara, (B) Ishihara, and (C) Whiting in the activation of carboxylic acids toward nucleophilic attack through complexation with arylboronic acids to form an acyloxy boronic acid.
Figure 4.
Figure 4.
Activation of oxygen atoms as nucleophiles by complexation with a borinic acid. Complexation of a diol with a boronic acid leads to a neutral complex and no additional electron density on the oxygen atoms. The anionic complex formed with a borinic acid leads to an increase in electron density on oxygen and its activation as a nucleophile.
Figure 5.
Figure 5.
Strategy for the in-situ formation of a chiral Brønsted acid from 2-carboxyphenylboronic acid and a chiral diol. Internal coordination of the carboxylic acid to the boronic acid increases the Brønsted acidity.
Figure 6.
Figure 6.
Change in C–H bond energies in rhamnopyranosides upon formation of a complex with diphenylborinic acid. Data were calculated in the gas phase with the B97-D3/Def2-TZVP level of theory.
Scheme 1.
Scheme 1.
Boronic Acid Catalyzed Dehydration of Biomass-Derived Glucose to 5-Hydroxymethylfurfural
Scheme 2.
Scheme 2.
Catalysis of Anhydride Formation by an o-Dialkylaminomethyl-Substituted Phenylboronic Acid.–
Scheme 3.
Scheme 3.
Boric Acid Catalyzed Formation of Benzimidazoles from Diamines and Carboxylic Acids
Scheme 4.
Scheme 4.
Boric Acid Catalyzed Synthesis of a 1,2,4-Triazolopyridinone
Scheme 5.
Scheme 5.
Stereoselective Catalysis of the Dehydration of an anti Aldol Reaction Product by a Borinic Acid
Scheme 6.
Scheme 6.
Boronic Acid-Accelerated Formation of Oximes for Bioconjugation
Scheme 7.
Scheme 7.
Hydrolysis of a Salicylaldehyde Imine, Catalyzed by Boric Acid or a Boronic Acid through the Stabilization of a Hemiaminal Intermediate
Scheme 8.
Scheme 8.
Catalysis of an Aldol Reaction by a Benzimidazole-Substituted Phenylboronic Acid
Scheme 9.
Scheme 9.
Aldol Addition Through Combined Enamine–Boronic Acid Catalysis by Homoboroproline
Scheme 10.
Scheme 10.
Catalysis of Isotetronic Acid Synthesis by a Borinic Acid
Scheme 11.
Scheme 11.
Boric Acid Catalyzed Biginelli Reaction for the Production of 3,4-Dihydropyirimidin-2(1H)-ones
Scheme 12.
Scheme 12.
Catalysis of a Three-Component Ugi Reaction by Boric Acid in Water
Scheme 13.
Scheme 13.
Boric Acid Catalyzed Synthesis of a Thiopyridine via a Three-Component Condensation
Scheme 14.
Scheme 14.
Solvent-Free Four-Component Condensation Catalyzed by Boric Acid and Water
Scheme 15.
Scheme 15.
Catalysis of a Three-Component Synthesis of a Tetrahydrobenzo[b]pyran by Phenylboronic Acid
Scheme 16.
Scheme 16.
Catalysis of a Three-Component Condensation by Pentafluorophenylboronic Acid
Scheme 17.
Scheme 17.
Arylboronic Acid Catalysts Reported by Yamamoto and Wang for the Formation of Amide Bonds
Scheme 18.
Scheme 18.
Boric Acid Catalyzed Selective Esterification of an α-Hydroxycarboxylic Acid
Scheme 19.
Scheme 19.
Catalytic Amidation of a β-Hydroxycarboxylic Acid using a Diboronic Acid Anhydride
Scheme 20.
Scheme 20.
Borate Ester-Catalyzed Amidation.
Scheme 21.
Scheme 21.
Boronic Acid Catalyzed Amidation
Scheme 22.
Scheme 22.
Borinic Acid Catalyzed Site-Selective Monoacylation of a Carbohydrate
Scheme 23.
Scheme 23.
Boronic Acid Catalyzed Site-Selective Monoacylation of a Carbohydrate
Scheme 24.
Scheme 24.
Borinic Acid Catalyzed Formylating Transamidation with DMF
Scheme 25.
Scheme 25.
Boronic Acid Catalyzed Beckmann Rearrangement
Scheme 26.
Scheme 26.
Boronic Acid Catalyzed Friedel–Crafts Alkylation
Scheme 27.
Scheme 27.
Synthesis of Asymmetric Diarylmethanes, Catalyzed by Ferroceniumboronic Acid
Scheme 28.
Scheme 28.
Indole Addition to Nitroolefins Through Boron-Assisted Brønsted Acidity
Scheme 29.
Scheme 29.
Boronic Acid Catalyzed Dehydrative Etherification.
Scheme 30.
Scheme 30.
Boron-Templated Acid Catalyzed Dimerization of Allylic Alcohols
Scheme 31.
Scheme 31.
Boronic Acid Catalyzed Allylation of an Oxime
Scheme 32.
Scheme 32.
Ether Exchange of Methoxynitroarenes Promoted by Phenylboronic Acid Pinacol Ester
Scheme 33.
Scheme 33.
Ene Carbocyclization of Pendant Alkynes, Catalyzed by a Boronic Acid
Scheme 34.
Scheme 34.
Boronic Acid Catalyzed Site-Selective Epoxide Aminolysis
Scheme 35.
Scheme 35.
Catalysis of Nitrocyclopropane Ring-Opening by a Urea-Substituted Arylboronic Acid
Scheme 36.
Scheme 36.
Boronic Acid-Catalyzed Desymmetrization of a 2-Aryl-1,3-propanediol
Scheme 37.
Scheme 37.
Catalysis of O-Glycosylation by an Imidazole-Substituted Phenylboronic Acid
Scheme 38.
Scheme 38.
Catalysis of O-Glycosylation by an p-Nitrophenylboronic Acid
Scheme 39.
Scheme 39.
Catalysis of C-Glycosidation by Boric Acid and Pyrrolidine
Scheme 40.
Scheme 40.
Phase-Transfer Catalysis of O-Glycosidation by Phenylboronic Acid
Scheme 41.
Scheme 41.
Boric Acid-Catalyzed aza-Michael Addition
Scheme 42.
Scheme 42.
Catalysis of an Enantioselective aza-Michael Addition by a BINOL Boronic Acid
Scheme 43.
Scheme 43.
Catalysis of an Asymmetric aza-Michael Addition by a Thiourea-Substituted Phenylboronic Acid
Scheme 44.
Scheme 44.
Boronic Acid-Catalyzed Reductive Alkylation of a Quinoline
Scheme 45.
Scheme 45.
Enantioselective 1,4-Addition Reaction, Catalyzed by a Boronic Acid and Chiral Amine.
Scheme 46.
Scheme 46.
Borinic Acid-Catalyzed Regioselective N-Alkylation of an Azole Heterocycle
Scheme 47.
Scheme 47.
Boronic Acid-Catalyzed [4 + 2] Cycloaddition
Scheme 48.
Scheme 48.
Boronic Acid-Catalyzed [3 + 2] Cycloaddition
Scheme 49.
Scheme 49.
Boronic Acid-Catalyzed [4 + 3] Cycloaddition
Scheme 50.
Scheme 50.
Borinic Acid-Catalyzed Epoxide Ring-Opening with (A) a Halide, (B) a Sulfonyl or Acyl Chloride,, and (C) a Semipinacol Rearrangement
Scheme 51.
Scheme 51.
Boronic Acid-Catalyzed Asymmetric Aziridination of an Imine
Scheme 52.
Scheme 52.
Boronic Acid Catalyzed Oxidation of a 1,2-Diol to an α-Hydroxy Ketone
Scheme 53.
Scheme 53.
Borinic Acid Catalyzed Oppenauer Oxidation of an Alcohol
Scheme 54.
Scheme 54.
Boronic Acid Catalyzed Site-Selective Photochemical Oxidation of an Unprotected Carbohydrate
Scheme 55.
Scheme 55.
Boronic Acid Catalyzed Reduction of an Amide with a Silane
Scheme 56.
Scheme 56.
Boronic Acid Promoted Selective Reduction of Aldehydes
Scheme 57.
Scheme 57.
Borinic Acid Catalyzed Reduction of Phosphine Oxides, Sulfoxides, and Amine N-Oxides
Scheme 58.
Scheme 58.
Catalysis of the Reductive Formylation of an Amine with Carbon Dioxide by a Sodium Phenylboronate Salt
Scheme 59.
Scheme 59.
Boronic Acid Catalyzed Synthesis of a Cyclic Carbonate from an Epoxide and CO2
Scheme 60.
Scheme 60.
Boronic Acid Catalyzed Site-Selective Silylation of a Pyranoside
Scheme 61.
Scheme 61.
Boric Acid Catalyzed Trimethylsilylation and Deprotection of an Alcohol
Scheme 62.
Scheme 62.
Hydrostannylation of an Alkyne, Promoted by Boric Acid
Scheme 63.
Scheme 63.
Photocatalytic Alkylation of a Carbohydrate, Directed by a Borinic Acid
Scheme 64.
Scheme 64.
Photocatalytic Oxidation of a Furanoside, Directed by a Boronic Acid
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