光电化学氧化C ((sp3) -H无活化碳化合物的化
Ping-Fu Zhong1, Jia-Lin Tu1, Yating Zhao2
1State Key Lab of Urban Water Resource and Environment, Harbin Institute of Technology (Shenzhen), Shenzhen, 518055, China.
Nature communications
|October 16, 2023
概括
这项研究引入了一种新的光电化学方法,用于C(sp3) -H玻里化,产生没有金属或氧化剂的有机化合物. 这种高效的过程为药物发现提供了一条可扩展的途径,以获得有价值的构建块.
科学领域:
- 有机化学 有机化学
- 合成化学 合成化学
- 摄影化学的使用.
背景情况:
- 有机化合物在有机合成中对于分子修饰至关重要.
- 将玻利基组纳入分子,特别是通过碳化合物的C(sp3) -H玻利化,是目前正在积极研究的一个领域.
研究的目的:
- 开发一种无金属和无氧化剂的氧化C(sp3) -H玻利化反应.
- 为了实现这一转换,利用光电化学策略.
主要方法:
- 开发一种光电化学策略,用于C(sp3) -H玻利化.
- 没有金属和氧化剂的反应条件.
主要成果:
- 证明了广泛的基质范围 (>57个例子),包括,化物,西兰,,,和.
- 实现了非常规的区域选择性,化发生在远端甲基组.
- 经过证明的操作简单性和可扩展性.
结论:
- 开发的方法提供了从简单的碳化合物中高价值的有机构建块的一步合成的可行性.
- 这种方法为药物发现和开发提供了重大机会.
相关概念视频
Regioselectivity and Stereochemistry of Hydroboration
8.2K
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...
8.2K
Hydroboration-Oxidation of Alkenes
8.3K
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.
8.3K
Alkynes to Aldehydes and Ketones: Hydroboration-Oxidation
18.2K
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.
18.2K
Radical Substitution: Hydrogenolysis of Alkyl Halides with Tributyltin Hydride
1.8K
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...
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...
1.8K
Photochemical Electrocyclic Reactions: Stereochemistry
1.8K
The absorption of UV–visible light by conjugated systems causes the promotion of an electron from the ground state to the excited state. Consequently, photochemical electrocyclic reactions proceed via the excited-state HOMO rather than the ground-state HOMO. Since the ground- and excited-state HOMOs have different symmetries, the stereochemical outcome of electrocyclic reactions depends on the mode of activation; i.e., thermal or photochemical.
Selection Rules: Photochemical Activation
Selection Rules: Photochemical Activation
1.8K
Radical Anti-Markovnikov Addition to Alkenes: Mechanism
3.8K
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...
3.8K


![[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)