Divergence from the classical hydroboration reactivity; boron containing materials through a hydroboration cascade of small cyclic dienes

Abstract

Quantitative dihydroboration of cyclic dienes leading to new, tunable boron-containing hydrocarbon polymeric materials.

Deviation from the anti-Markovnikov rule: a computational study of the regio- and stereoselectivity of diene hydroboration reactions

“…1), with experimental data available from previous work for eight [17]. Hydroboration of the initial substrates yields a monosubstituted species, which can further react to form various fully hydroborated products, depending on the ratio of the borane and the reactant diene [17]. The amount of diene available to react affects the ratios of the resulting products, and its excess might only allow the first step of the reaction to proceed and thus yield a monosubstituted olefin.…”

“…1), with experimental data available from previous work for eight [17]. Hydroboration of the initial substrates yields a monosubstituted species, which can further react to form various fully hydroborated products, depending on the ratio of the borane and the reactant diene [17].…”

“…It was previously thought that only partial hydroboration takes place in dienes, resulting in unsaturated reaction products described by Brown and Bhat [18]. Our recent study [17] demonstrated that hydroboration was not limited to one of the double bonds, and that in fact polymers formed as a result of fully saturated, boron-containing hydrocarbons cross-linking together. We report here the results of quantum chemical calculations of hydroboration reactions, focusing on the regiospecificity of the obtained products.…”

“…Simplified explanations of hydroboration use the positions of resulting hydroxyl groups to assign the positions of boron attachment and infer the reaction mechanism. This, however, is known to be inaccurate, as an oxidized product can arise from several different organoboranes [17], and a mechanistic explanation is missing that describes the complete process, including the specific identity of the unoxidized compounds [17]. In addition, owing to the high reactivity and sensitivity of the direct hydroboration products to oxidation, their study using solely analytical techniques is highly challenging.…”

“…13 Page 2 of 14 hydroboration products in the final product specificity, previous studies have mainly focused on the subsequent reactions, such as their oxidation to form alcohols, and the direct unoxidized hydroboration products have until now received little attention [15][16][17].…”