H結合認識のための多用途の自己適応ボロン酸:離散型からポリマー型超分子へ
Irene Georgiou1, Simon Kervyn1, Alexandre Rossignon1,2
1Department of Chemistry, University of Namur (UNamur) , Rue de Bruxelles 61, 5000 Namur, Belgium.
Journal of the American Chemical Society
|January 5, 2017
まとめ
アロマチックなボロン酸は,新しい二重水素結合複合体を形成し,超分子化学と材料科学での使用を拡大しています. これらの研究はユニークな"T形"とポリマー構造を明らかにし,新しい触媒と材料への道を切り開きます.
科学分野:
- 超分子化学
- 材料科学
- 有機化学
背景:
- ボロン酸は独特のダイナミック・コバルント反応性を表している.
- 材料と超分子化学のためのアリルボロン酸への関心が高まっている.
- 彼らの水素結合能力は まだ十分に研究されていない
研究 の 目的:
- アロマティック・ボロン酸の水素結合複合性を研究する.
- 二重H結合のDD·AA型複合体の形成を調査する.
- 溶液と固体状態の両方でこれらの複合体を研究する.
主な方法:
- アソシエーション定数 (Ka) を決定するための溶液結合試験.
- 固体構造 (二次,三次複合体) を分析するための結晶化.
- 複合形成の光譜と結晶分析
主要な成果:
- オーソ置換ボロン酸のKaの最初の決定 (300-6900M-1).
- フロントルH結合で安定したシンシンコンフォーマーの識別
- 置換に基づく"平ら"および"T形"複合体の観察.
- ディボロン酸とテトラザナフタゼンから超分子H結合のポリマーリボン形成
結論:
- アロマチックなボロン酸は,よく定義された二重H結合複合体を形成することができる.
- ボロン酸の形状の柔軟性は複雑な構造を決定する.
- これらの発見は,金属なしの触媒と有機結晶工学の可能性を秘めています.
関連する概念動画
Regioselectivity and Stereochemistry of Hydroboration
9.6K
A significant aspect of hydroboration–oxidation is the regio- and stereochemical outcome of the reaction.
Hydroboration proceeds in a concerted fashion with the attack of borane on the π bond, giving a cyclic four-centered transition state. The –BH2 group is bonded to the less substituted carbon and –H to the more substituted carbon. The concerted nature requires the simultaneous addition of –H and –BH2 across the same face of the alkene giving syn stereochemistry.
Hydroboration proceeds in a concerted fashion with the attack of borane on the π bond, giving a cyclic four-centered transition state. The –BH2 group is bonded to the less substituted carbon and –H to the more substituted carbon. The concerted nature requires the simultaneous addition of –H and –BH2 across the same face of the alkene giving syn stereochemistry.
9.6K
Hydroboration-Oxidation of Alkenes
11.9K
In addition to the oxymercuration–demercuration method, which converts the alkenes to alcohols with Markovnikov orientation, a complementary hydroboration-oxidation method yields the anti-Markovnikov product. The hydroboration reaction, discovered in 1959 by H.C. Brown, involves the addition of a B–H bond of borane to an alkene giving an organoborane intermediate. The oxidation of this intermediate with basic hydrogen peroxide forms an alcohol.
11.9K
Hydrogen Bonds
15.6K
A hydrogen bond is formed when a weakly positive hydrogen atom already bonded to one electronegative atom (for example, the oxygen in the water molecule) is attracted to another electronegative atom from another polar molecule, such as water (H2O), hydrogen fluoride (HF), or ammonia (NH3). The huge electronegativity difference between the H atom (2.1) and the atom to which it is bonded (4.0 for an F atom, 3.5 for an O atom, or 3.0 for an N atom), combined with the very small size of an H atom...
15.6K
Hydrogen Bonds
135.9K
Hydrogen bonds are weak attractions between atoms that have formed other chemical bonds. One of these atoms is electronegative, like oxygen, and has a partial negative charge. The other is a hydrogen atom that has bonded with another electronegative atom and has a partial positive charge.
Hydrogen Bonds Control the World!
Because hydrogen has very weak electronegativity when it binds with a strongly electronegative atom, such as oxygen or nitrogen, electrons in the bond are unequally shared....
Hydrogen Bonds Control the World!
Because hydrogen has very weak electronegativity when it binds with a strongly electronegative atom, such as oxygen or nitrogen, electrons in the bond are unequally shared....
135.9K
Alkynes to Aldehydes and Ketones: Hydroboration-Oxidation
21.7K
Introduction
One of the convenient methods for the preparation of aldehydes and ketones is via hydration of alkynes. Hydroboration-oxidation of alkynes is an indirect hydration reaction in which an alkyne is treated with borane followed by oxidation with alkaline peroxide to form an enol that rapidly converts into an aldehyde or a ketone. Terminal alkynes form aldehydes, whereas internal alkynes give ketones as the final product.
One of the convenient methods for the preparation of aldehydes and ketones is via hydration of alkynes. Hydroboration-oxidation of alkynes is an indirect hydration reaction in which an alkyne is treated with borane followed by oxidation with alkaline peroxide to form an enol that rapidly converts into an aldehyde or a ketone. Terminal alkynes form aldehydes, whereas internal alkynes give ketones as the final product.
21.7K
Noncovalent Attractions in Biomolecules
65.7K
Noncovalent attractions are associations within and between molecules that influence the shape and structural stability of complexes. These interactions differ from covalent bonding in that they do not involve sharing of electrons.
Four types of noncovalent interactions are hydrogen bonds, van der Waals forces, ionic bonds, and hydrophobic interactions.
Hydrogen bonding results from the electrostatic attraction of a hydrogen atom covalently bonded to a strong-electronegative atom like oxygen,...
Four types of noncovalent interactions are hydrogen bonds, van der Waals forces, ionic bonds, and hydrophobic interactions.
Hydrogen bonding results from the electrostatic attraction of a hydrogen atom covalently bonded to a strong-electronegative atom like oxygen,...
65.7K


