アルキルボロナートエステルの触媒的非対称合成のための一般的なモジュール法
Jens Schmidt1, Junwon Choi1, Albert Tianxiang Liu1
1Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, CA 91125, USA.
まとめ
研究者は,ステレオコンバージェントアルキル-アルキル結合のためのキラルニッケル触媒を用いた新しい方法を開発しました. これは,医薬品科学と有機化学合成のための貴重なエナチオ濃縮アルキルボラネートエステルへのアクセスを提供します.
科学分野:
- 有機化学
- カタリシス
- 合成化学
背景:
- アルキルボロン化合物は,医薬品科学と有機化学において重要な中間物質である.
- ステレオ化学的に制御されたアルキルボロナートエステルの合成は非常に価値があります.
- 炭素-ボロン結合の変換により,様々な合成用途が可能です.
研究 の 目的:
- 抗酸化アルキルボロナートエステルを合成するための新しい方法を開発する.
- 簡単に手に入る材料を使って,ステレオコンバージェントアルキル-アルキルカップリングを実現する.
- 合成された化合物の有用性をさらなる合成変換で実証する.
主な方法:
- 結合反応にキラルニッケル触媒を使用した.
- ラセミカルα-ハロボロナートとオルガノジン反応剤を基板として使用した.
- 軽度な条件下で実施した反応.
主要な成果:
- アルキル-アルキル結合のステレオ収束を達成した.
- エナチオ濃縮アルキルボロナートエステルの多様性を生成した.
- チラル・ボロンを含む分子への直接的なアクセスが示された.
結論:
- 開発されたニッケル触媒方式は,エナチオ濃縮アルキルボラネートエステルへの効率的な経路を提供します.
- これらのキラルボロン化合物は有機合成における多用途な構成要素です.
- 薬剤の発見と開発のための貴重な中間材料へのアクセスを促進します.
関連する概念動画
Alkylation of β-Ketoester Enolates: Acetoacetic Ester Synthesis
4.8K
Acetoacetic ester synthesis is a method to obtain ketones from alkyl halides and β-keto esters. The reaction occurs in the presence of an alkoxide base that abstracts the acidic proton of the β-keto esters. The step results in an enolate ion which is doubly stabilized. The enolate then reacts with an alkyl halide via the SN2 process to produce an alkylated ester intermediate with a new C–C bond. The hydrolysis of the intermediate, followed by acidification, results in an...
4.8K
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
Alkylation of β-Diester Enolates: Malonic Ester Synthesis
4.3K
Malonic ester synthesis is a method to obtain α substituted carboxylic acids from ꞵ-diesters such as diethyl malonate and alkyl halides.
4.3K
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
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
α-Alkylation of Ketones via Enolate Ions
4.0K
Ketones with α protons are deprotonated by strong bases like lithium diisopropylamide (LDA) to form enolate ions. The anion is stabilized by resonance, and its hybrid structure exhibits negative charges on the carbonyl oxygen and the α carbon. This ambident nucleophile can attack an electrophile via two possible sites: the carbonyl oxygen, known as O-attack, or the α carbon, known as C-attack. The nucleophilic attack via the carbanionic site is preferred. This is due to the...
4.0K


