269409-83-8Relevant academic research and scientific papers
Examination of pinanediol-boronic acid ester formation in aqueous media: Relevance to the relative stability of trigonal and tetrahedral boronate esters
Flores-Alamo, Marcos,Martínez-Aguirre, Mayte A.,Medrano, Felipe,Yatsimirsky, Anatoly K.
, p. 2716 - 2726 (2020)
The interaction of pinanediol with 2-fluorophenylboronic acid and several other substituted phenylboronic acids was studied in 40% vol. aqueous acetonitrile by 1H and 11B NMR, potentiometric and spectrophotometric titrations at variable pH values. The experimental results reveal the formation of a very stable trigonal ester (Ktrig ≈ 2 × 104 M-1) and a significantly less stable tetrahedral hydroxocomplex (Ktet ≈ 5 × 103 M-1) in contrast to the traditionally observed inverted order of stabilities Ktrig tet. Comparison of the crystal structure of the trigonal ester isolated from aqueous acetonitrile with the DFT simulated structure of the respective hydroxocomplex shows that an unusual order of stabilities Ktrig > Ktet is observed in spite of the existence of the usual strain release effect in the O-B-O angle considered responsible for the typically observed increased stability of the tetrahedral hydroxocomplex. A complementary study of the stability of the six-membered cyclic boronate esters of chromotropic acid demonstrated the order Ktrig ? Ktet although the strain was absent in these esters. The results for m-, p-substituted phenylboronic acids show that the stability of both five- and six-membered trigonal esters formed with pinanediol and chromotropic acid, respectively, is insensitive to electronic effects but the electron accepting substituents stabilize the hydroxocomplexes. It follows from the whole set of results that Ktet can be much larger than Ktrig in the absence of the strain, but with a sufficiently acidic diol, and that the presence of the strain does not necessarily make Ktet larger than Ktrig for a less acidic diol with a purely saturated hydrocarbon backbone. Thus, the electronic effects manifested in the acidity of the diol appear to be more significant than the strain release effect in determining the Ktet/Ktrig ratio.
Hydroboronation process
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Page column 43, (2010/02/05)
The invention relates to processes for the synthesis of aryl or alkene borates which comprises reacting: (i) an olefinic compound having a halogen or halogen-like substituent in a vinylic substitution position, or (ii) an aromatic ring having a halogen or halogen-like substituent in a ring substitution position, with a disubstituted monohydroborane in the presence of a Group 8-11 metal catalyst. The invention also relates to the use of these borates in coupling reactions. The invention further relates to certain disubstituted monohydroboranes and aryl or alkene borates.
