铁玻酸催化了酒精与碳和基酸盐和酸盐核友的脱氧化合
Jake J Blackner1, Deirdre M Rooney2, Joshua W Hollett2
1Department of Chemistry, University of Manitoba, Winnipeg, Manitoba R3T 2N2, Canada.
The Journal of organic chemistry
|June 7, 2023
概括
一种新的酸催化反应使得醇与有机素的高效去氧化合,形成新的碳-碳和碳-键. 这种方法在温和条件下提供高产量和广泛的基质范围.
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,开发高效的碳-碳和碳-键形成方法至关重要.
- 脱氧化合反应提供了一种途径,通过去除基组来功能化酒精.
研究的目的:
- 开发一种新的酸催化反应,用于直接去氧化合的酒精.
- 探索在这种转化中使用有机和三甲酸作为核友的用途.
主要方法:
- 使用铁玻酸六甲胺盐作为催化剂.
- 研究了各种π活性酒精与有机和三甲酸核友的结合.
- 进行计算研究以阐明反应机制.
主要成果:
- 实现了高效的碳-碳和碳-键形成.
- 与三基酸盐相比,有机基提供了更高的产量和更广泛的基板范围.
- 与基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基
结论:
- 开发了一种通用且高效的酸催化脱氧化合方法.
- 这种反应对各种有机基核友有效,包括基,基和基三甲基.
- 计算研究支持解释立体化学保留的机制.
相关概念视频
Hydroboration-Oxidation of Alkenes
8.5K
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.
8.5K
Preparation of Alcohols via Addition Reactions
6.3K
Overview
The acid-catalyzed addition of water to the double bond of alkenes is a large-scale industrial method used to synthesize low-molecular-weight alcohols. An acidic atmosphere is required to allow the hydrogen in the water molecule to act as an electrophile and attack the double bond in an alkene. The addition of a proton to the double bond creates a carbocation intermediate. The proton preferentially bonds to the less substituted end of the double bond to create a more stable carbocation...
The acid-catalyzed addition of water to the double bond of alkenes is a large-scale industrial method used to synthesize low-molecular-weight alcohols. An acidic atmosphere is required to allow the hydrogen in the water molecule to act as an electrophile and attack the double bond in an alkene. The addition of a proton to the double bond creates a carbocation intermediate. The proton preferentially bonds to the less substituted end of the double bond to create a more stable carbocation...
6.3K
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
Alkynes to Aldehydes and Ketones: Hydroboration-Oxidation
18.4K
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.
18.4K
Aldol Condensation with β-Diesters: Knoevenagel Condensation
3.1K
The Knoevenagel condensation is an aldol-type reaction involving the condensation of aldehydes or ketones with active methylene compounds such as β-diesters to produce substituted olefins.
3.1K
Alcohols from Carbonyl Compounds: Reduction
10.5K
Reduction is a simple strategy to convert a carbonyl group to a hydroxyl group. The three major pathways to reduce carbonyls to alcohols are catalytic hydrogenation, hydride reduction, and borane reduction.
Catalytic hydrogenation is similar to the reduction of an alkene or alkyne by adding H2 across the pi bond in the presence of transition metal catalysts like Raney Ni, Pd–C, Pt, or Ru. Aldehydes and ketones can be reduced by this method, often under mild to moderate heat (25–100°C) and...
Catalytic hydrogenation is similar to the reduction of an alkene or alkyne by adding H2 across the pi bond in the presence of transition metal catalysts like Raney Ni, Pd–C, Pt, or Ru. Aldehydes and ketones can be reduced by this method, often under mild to moderate heat (25–100°C) and...
10.5K


