銅 ((I) -触媒化されたラディカル-リレー反応 活性化されていないオレフィンの分子間1,2-アルキルボリレーションを可能にする
Sota Akiyama1, Natsuki Oyama1, Tsubura Endo1
1Division of Applied Chemistry, Graduate School of Engineering, Hokkaido University, Sapporo, Hokkaido 060-8628, Japan.
Journal of the American Chemical Society
|March 30, 2021
まとめ
この研究は,アルキル電極を用いた非活性化オレフィンに対する最初の触媒的ラジカルリレーアルキルボリレーションを導入する. この方法は,アルキルとボリル群を二重結合に効率的に配置し,競合する置換反応を克服します.
科学分野:
- 有機化学
- カタリシス
- 合成方法論
背景:
- アルキルボリレーション反応は,オルガノボロン化合物の合成に不可欠である.
- 既存の方法はしばしば活性化されていないオレフィンと闘い,特定の基板を必要とします.
- ラジカル・リレーメカニズムは,C−C結合形成のための新しい経路を提供します.
研究 の 目的:
- 活性化されていないオレフィンの最初の触媒的分子間1,2-アルキルボリレーションを開発する.
- アルキル電子とビスコラトジボロンを含む 根源リレーメカニズムを使用する.
- オレフィン二重結合の領域選択的機能化を実現する.
主な方法:
- 分子間アルキルボリレーションのための触媒システムを使用する.
- 反応を容易にするために 根源リレーメカニズムを利用する.
- 競争するボリル置換を克服し,要求の高いアルキル電極を使用します.
主要な成果:
- 活性化されていないオレフィンの触媒的分子間1,2-アルキルボリレーションが成功しました.
- C=C二重結合にアルキルとボリル群の地域選択的導入
- 多様なアルキル基 (ジェム・ディフローロ,モノフローロ,三次性,二次性) の導入が実証されている.
結論:
- この研究は,オレフィンの1,2-非機能化のための新しい合成経路を確立しています.
- ラジカルリレーアプローチはアルキルボリレーションの強力な戦略を提供します.
- この方法は,様々なアルキル機能の設置に広く適用できます.
関連する概念動画
Radical Anti-Markovnikov Addition to Alkenes: Mechanism
4.3K
The reaction of hydrogen bromide with alkenes in the presence of hydroperoxides or peroxides proceeds via anti-Markovnikov addition. The radical chain reaction comprises initiation, propagation, and termination steps.
The mechanism starts with chain initiation, which involves two steps. In the first chain initiation step, a weak peroxide bond is homolytically cleaved upon mild heating to form two alkoxy radicals. In the second initiation step, a hydrogen atom is abstracted by the alkoxy...
The mechanism starts with chain initiation, which involves two steps. In the first chain initiation step, a weak peroxide bond is homolytically cleaved upon mild heating to form two alkoxy radicals. In the second initiation step, a hydrogen atom is abstracted by the alkoxy...
4.3K
Hydroboration-Oxidation of Alkenes
9.8K
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.
9.8K
Radical Substitution: Allylic Bromination
5.9K
In organic synthesis, the formation of products can be altered by changing the reaction conditions. For example, a dibromo addition product is formed when propene is treated with bromine at room temperature. In contrast, propene undergoes allylic substitution in non-polar solvents at high temperatures to give 3-bromopropene. In order to avoid the addition reaction, the bromine concentration must be kept as low as possible throughout the reaction. This can be achieved using N-bromosuccinimide...
5.9K
Radical Reactivity: Nucleophilic Radicals
2.4K
Radicals adjacent to electron-donating groups are called nucleophilic radicals. These radicals readily react with electrophilic alkenes. The SOMO–LUMO interactions are the driving force for the reaction, where the high-energy SOMO of the electron-rich, nucleophilic radicals interacts with the low-energy LUMO of the electron-deficient, electrophilic alkenes. Such SOMO–LUMO interactions are the basis of reactive radical traps, affecting the selectivity in radical reactions. For...
2.4K
Alkynes to Aldehydes and Ketones: Hydroboration-Oxidation
19.5K
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.
19.5K
Alkenes via Reductive Coupling of Aldehydes or Ketones: McMurry Reaction
2.1K
The radical dimerization of ketones or aldehydes gives vicinal diols through a pinacol coupling reaction. However, the behavior of titanium metals used for the reaction as a source of electrons is unusual. When the reaction is carried out in the presence of titanium, diols can be isolated at low temperatures. Else titanium further reacts with diols, forming alkenes through the McMurry reaction.
2.1K


![[DPEPhosbcpCu]PF6: A General and Broadly Applicable Copper-Based Photoredox Catalyst](/_next/image?url=https%3A%2F%2Fcloudfront.jove.com%2FCDNSource%2Fteasers%2F59739.jpg&w=3840&q=50)