通过可见光驱动的化,通过催化,将C{sp2}-O键与基化
Itsuki Nohira1, Shisei Yamazaki1, Shiho Ishigaki1
1Department of Chemical Science and Engineering, Institute of Science Tokyo, O-okayama, Meguro-ku, Tokyo 152-8550, Japan.
Organic letters
|November 10, 2025
概括
一种新方法使得使用西尔博兰和催化剂能够高效地化和的C-O键. 蓝色LED光加速了反应,在温和的条件下扩大了兼容的silyl组.
科学领域:
- 有机化学 有机化学
- 催化剂是一种催化剂.
- 合成方法论 合成方法论
背景情况:
- 在有机合成中,C-O键化是至关重要的.
- 开发通用,高效和温和的方法仍然是一个挑战.
- 现有的方法往往缺乏广泛的基质或基组范围.
研究的目的:
- 开发一种新且高效的C(sp2) -O键化方法.
- 在温和的反应条件下实现广泛的基群耐受性.
- 为了利用催化剂进行C-O键裂解.
主要方法:
- 使用具有特定残基 (-OPO3tBu2, -OC(O) NiPr2) 的醇和醇衍生物.
- 使用西利博兰作为化剂.
- 使用没有添加配体的Ni(0) 催化剂进行反应.
- 研究蓝色LED辐射的影响.
主要成果:
- 通过C-O键裂变实现了成功的化.
- 反应表明对广泛的基基具有耐受性.
- 蓝色LED辐射显著加快了反应速度.
- 该过程在温和和环境条件下运行.
结论:
- 已经建立了一种通用且高效的Ni(0) -催化C-O化方法.
- 反应由蓝光促进,提高了它的适用性.
- 这种方法为在温和条件下引入基组提供了有价值的工具.
相关概念视频
Preparation and Reactions of Sulfides
5.7K
Sulfides are the sulfur analog of ethers, just as thiols are the sulfur analog of alcohol. Like ethers, sulfides also consist of two hydrocarbon groups bonded to the central sulfur atom. Depending upon the type of groups present, sulfides can be symmetrical or asymmetrical. Symmetrical sulfides can be prepared via an SN2 reaction between 2 equivalents of an alkyl halide and one equivalent of sodium sulfide.
5.7K
Oxidation of Alkenes: Syn Dihydroxylation with Osmium Tetraoxide
12.5K
Alkenes are converted to 1,2-diols or glycols through a process called dihydroxylation. It involves the addition of two hydroxyl groups across the double bond with two different stereochemical approaches, namely anti and syn. Dihydroxylation using osmium tetroxide progresses with syn stereochemistry.
12.5K
Radical Substitution: Allylic Bromination
6.4K
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...
6.4K
Reduction of Alkynes to cis-Alkenes: Catalytic Hydrogenation
8.9K
Introduction
Like alkenes, alkynes can be reduced to alkanes in the presence of transition metal catalysts such as Pt, Pd, or Ni. The reaction involves two sequential syn additions of hydrogen via a cis-alkene intermediate.
Like alkenes, alkynes can be reduced to alkanes in the presence of transition metal catalysts such as Pt, Pd, or Ni. The reaction involves two sequential syn additions of hydrogen via a cis-alkene intermediate.
8.9K
α-Alkylation of Ketones via Enolate Ions
3.7K
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...
3.7K
Radical Substitution: Hydrogenolysis of Alkyl Halides with Tributyltin Hydride
2.2K
Radical substitution reactions can be used to remove functional groups from molecules. The hydrogenolysis of alkyl halides is one such reaction, where the weak Sn–H bond in tributyltin hydride reacts with alkyl halides to form alkanes. Here, the reagent Bu3SnH yields tributyltin halide as a byproduct.
The bonds formed in this reaction are stronger than the bonds broken, making it energetically favorable. The reaction follows a radical chain mechanism similar to radical halogenation reactions,...
The bonds formed in this reaction are stronger than the bonds broken, making it energetically favorable. The reaction follows a radical chain mechanism similar to radical halogenation reactions,...
2.2K


