Crystal engineering gone awry and the emergence of the boronic acid–carboxylate synthon

Aakeröy, Christer B.; Desper, John; Levin, Brock

doi:10.1039/b417896c

Cited by 55 publications

(29 citation statements)

References 32 publications

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“…It is noteworthy that the enhanced Lewis acidity of boronic esters plays a key role in these functions. Furthermore, boronic acids and their derivatives are also more and more often utilized in supramolecular chemistry (Aakerö y et al, 2004;Cô té et al, 2005;Nishiyabu et al, 2011b;Durka et al, 2013) and crystal engineering (Pedireddi & SeethaLekshmi, 2004;Aakerö y et al, 2005;Varughese et al, 2011;Cyrań ski et al, 2012). Accordingly, the information about their molecular geometry in crystals derived by the structure correlation method can contribute to these fields.…”

Section: Introductionmentioning

confidence: 99%

Geometry of trigonal boron coordination sphere in boronic acids derivatives – a bond-valence vector model approach

Czerwińska

Madura

Zachara

2016

Acta Crystallogr Sect B

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The systematic analysis of the geometry of three-coordinate boron in boronic acid derivatives with a common [CBO2] skeleton is presented. The study is based on the bond-valence vector (BVV) model [Zachara (2007). Inorg. Chem. 46, 9760-9767], a simple tool for the identification and quantitative estimation of both steric and electronic factors causing deformations of the coordination sphere. The empirical bond-valence (BV) parameters in the exponential equation [Brown & Altermatt (1985). Acta Cryst. B41, 244-247] rij and b, for B-O and B-C bonds were determined using data deposited in the Cambridge Structural Database. The values obtained amount to rBO = 1.364 Å, bBO = 0.37 Å, rBC = 1.569 Å, bBC = 0.28 Å, and they were further used in the calculation of BVV lengths. The values of the resultant BVV were less than 0.10 v.u. for 95% of the set comprising 897 [CBO2] fragments. Analysis of the distribution of BVV components allowed for the description of subtle in- and out-of plane deviations from the `ideal' (sp(2)) geometry of boron coordination sphere. The distortions specific for distinct groups of compounds such as boronic acids, cyclic and acyclic esters, benzoxaboroles and hemiesters were revealed. In cyclic esters the direction of strains was found to be controlled by the ring size effect. It was shown that the syn or anti location of substituents on O atoms is decisive for the deformations direction for both acids and acyclic esters. The greatest strains were observed in the case of benzoxaboroles which showed the highest deviation from the zero value of the resultant BVV. The out-of-plane distortions, described by the vz component of the resultant BVV, were ascertained to be useful in the identification of weak secondary interactions on the fourth coordination site of the boron centre.

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Section: Introductionmentioning

confidence: 99%

Geometry of trigonal boron coordination sphere in boronic acids derivatives – a bond-valence vector model approach

Czerwińska

Madura

Zachara

2016

Acta Crystallogr Sect B

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“…Experimentally it can be difficult to obtain pure samples of some phenylboronic acids that actually have the formula R–B(OH) 2 because they often separate from aqueous solutions as hydrates that undergo dehydration to yield boroxines [49, 50]; for example, Rogowska, et al . [51] reported recently that their attempts to determine the crystal structure of p -fluorophenylboronic acid failed because the system transformed to tris(4-fluorophenyl)boroxine.…”

Section: Resultsmentioning

confidence: 99%

Monosubstituted Phenylboronic Acids, R–B(OH)2 (R = C6H5, C6H4CH3, C6H4NH2, C6H4OH, and C6H4F): A Computational Investigation

Rao¹,

Larkin²,

Bock³

2016

Struct Chem

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Phenylboronic acids (PBAs) are an important class of compounds with diverse applications in synthetic, biological, medicinal, and materials chemistry. In this investigation we report structural and thermochemical parameters for several monosubstituted ortho, meta, and para PBAs, R–B(OH)2 (R = C6H5, C6H4CH3, C6H4NH2, C6H4OH, and C6H4F). Equilibrium geometries of all the PBAs discussed in this article were obtained using second-order Møller-Plesset perturbation theory (MP2) with the Dunning-Woon aug-cc-pVDZ basis set; heats of formation (HOF) were calculated at the Gaussian-3 (G3) level of theory. The endo-exo conformers of all the positional isomers of these PBAs were lowest in energy. Using HOF for the monosubstituted PBAs calculated at the G3 level of theory, in conjunction with the experimental HOF for benzene, toluene, aniline, phenol, and fluorobenzene, the values of normalΔH2980 for the transfer processes C6H6 + C6H4X–B(OH)2 → C6H5X + C6H5–B(OH)2 (X = CH3, NH2, OH, and F) are found to be in good agreement with values of normalΔH2980 calculated at the MP2(FC)/aug-cc-pVTZ//MP2(FC)/aug-cc-pVTZ computational level; the bonding in the reactants and products for these transfer reactions are well-matched and thermochemical calculations at this level are expected to be very accurate, providing checks on the G3 HOF calculations.

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“…The utility of boronic acids in noncovalent synthesis has not been studied extensively, although this class of compounds have been efficiently employed in organic synthesis as chemical building blocks and intermediates 34, 35. Further, pharmaceutical co‐crystals involving boronic acids are unknown in the literature.…”

Section: Resultsmentioning

confidence: 99%

Molecular Complexes of Alprazolam with Carboxylic Acids, Boric Acid, Boronic Acids, and Phenols. Evaluation of Supramolecular Heterosynthons Mediated by a Triazole Ring✩✩Additional Supporting Information may be found in the online version of this article.

Varughese

Azim

Desiraju

2010

Journal of Pharmaceutical Sciences

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Crystal engineering gone awry and the emergence of the boronic acid–carboxylate synthon

Cited by 55 publications

References 32 publications

Geometry of trigonal boron coordination sphere in boronic acids derivatives – a bond-valence vector model approach

Geometry of trigonal boron coordination sphere in boronic acids derivatives – a bond-valence vector model approach

Monosubstituted Phenylboronic Acids, R–B(OH)2 (R = C6H5, C6H4CH3, C6H4NH2, C6H4OH, and C6H4F): A Computational Investigation

Molecular Complexes of Alprazolam with Carboxylic Acids, Boric Acid, Boronic Acids, and Phenols. Evaluation of Supramolecular Heterosynthons Mediated by a Triazole Ring✩✩Additional Supporting Information may be found in the online version of this article.

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