フレストラテッド・ルイス・ペア・デリベート η2-フォルミル・ボランによる一酸化炭素結合反応
Qiu Sun1, Constantin G Daniliuc1, Klaus Bergander1
1Organisch-Chemisches Institut, Westfälische Wilhelms-Universität Münster, Corrensstraße 40, 48149 Münster, Germany.
Journal of the American Chemical Society
|September 13, 2021
まとめ
新しい η2 - フォーマルボランシステムは,一酸化炭素の結合を可能にする,挫折したルイスペアとして作用する. これは独特のボリル化エンディオラートと希少なマクロサイクルシリコンエンディオラートにつながる.
科学分野:
- オーガノボロン化学
- 挫折したルイス・ペア・ケミストリー
- 炭素化反応
背景:
- フレストラテッド・ルイス・ペア (FLP) は 独特の化学変換を可能にする 反応性のある種です
- 炭化反応は貴重な有機化合物を合成するのに不可欠です.
- ボラン化学は,触媒と材料科学で多様なアプリケーションを提供しています.
研究 の 目的:
- 新しい η2 - フォーマルボラン系を合成し,特徴づけること.
- このシステムの反応性を調査する 挫折したC・B・ルイス・ペアとして
- 新しい炭素-酸素およびシリコンを含む化合物の形成を調査する.
主な方法:
- 周辺のP/BHの炭素化により,ルイス・ペアが挫折した.
- 二酸化炭素,フェニリソシアネート,およびB ((C6F5) 3との反応.
- 反応産物の特徴は,スペクトロスコーピック技術を用いて決定する.
主要な成果:
- η2−ホルミルボラン系 (3) が成功して合成された.
- 化合物3は,CO2とフェニリソシアネートとのC/Bルイスペアの活動が挫折したことを示した.
- 二つのCO系単位の結合が達成され,二重O型ボリオラートが形成された (13).
- 希少なマクロサイクルシリコンエンディオラートは,シランで処理した後に得られた.
結論:
- 開発された η2−フォーミルボラン系は,CO活性化および結合のための多用途反応剤である.
- この研究は,挫折したルイス・ペア化学の範囲を広げています.
- 新種のボリル化エンディオラートとシリコンエンディオラートが合成され,新しい合成経路が浮き彫りにされた.
関連する概念動画
Hydroboration-Oxidation of Alkenes
9.4K
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.
9.4K
Regioselectivity and Stereochemistry of Hydroboration
8.6K
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...
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...
8.6K
Benzene to 1,4-Cyclohexadiene: Birch Reduction Mechanism
2.4K
Birch reduction uses solvated electrons as reducing agents. The reaction converts benzene to 1,4-cyclohexadiene. The reaction proceeds by the transfer of a single electron to the ring to form a benzene radical anion. This anion is highly basic—it abstracts a proton from the alcohol to form a cyclohexadienyl radical. Another single electron transfer gives the cyclohexadienyl anion. A proton transfer from the alcohol forms 1,4-cyclohexadiene. Since this reduction occurs via radical anion...
2.4K
Alkynes to Aldehydes and Ketones: Hydroboration-Oxidation
19.3K
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.
19.3K
Hybridization of Atomic Orbitals I
52.7K
The mathematical expression known as the wave function, ψ, contains information about each orbital and the wavelike properties of electrons in an isolated atom. When atoms are bound together in a molecule, the wave functions combine to produce new mathematical descriptions that have different shapes. This process of combining the wave functions for atomic orbitals is called hybridization and is mathematically accomplished by the linear combination of atomic orbitals. The new orbitals that...
52.7K
Exceptions to the Octet Rule
31.4K
Many covalent molecules have central atoms that do not have eight electrons in their Lewis structures. These molecules fall into three categories:
31.4K


