一种高度选择性的催化方法,用于氧化C-H键的功能化
Allison R Dick1, Kami L Hull, Melanie S Sanford
1Department of Chemistry, University of Michigan, 930 North University Avenue, Ann Arbor, Michigan 48109-1055, USA.
Journal of the American Chemical Society
|February 26, 2004
概括
一种新的催化方法使得和中C-H键的选择性功能化成为可能. 这种实用方法在温和条件下将碳键转化为,和化.
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:
- 碳- (C-H) 键的直接功能化仍然是有机合成的一个重大挑战.
- 开发用于C-H激活的实用和选择性方法对于高效的分子构造至关重要.
- 催化为CH功能化策略提供了一个强大的平台.
研究的目的:
- 引入一种新和实用的 ((II) 催化方法,用于氧化功能化和.
- 为了实现C-H键的区域和化学选择性转化.
- 探索这种新型合成转化的范围和机制.
主要方法:
- 使用 ((II) 催化剂进行氧化功能化反应.
- 使用指导组 (例如,皮里丁,阿佐,皮拉,伊胺衍生物) 来指导C-H键的激活.
- 研究各种氧化剂和反应条件,以优化选择性和产量.
主要成果:
- 在一系列的烯和基基底物中成功实现了C-H键的区域和化学选择性功能化.
- 证明了C-H键的转化为,和烯化物.
- 已建立适合不同基质和定向组的温和反应条件.
结论:
- 开发的Pd(II) 催化方法为选择性C-H键功能化提供了一个高度实用的方法.
- 反应表现出广泛的基质范围和对各种导向组的耐受性.
- 已经提出了一个初步的催化循环,为反应机制提供了洞察力.
相关概念视频
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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.
Oxidation of Alkenes: Anti Dihydroxylation with Peroxy Acids
Diols are compounds with two hydroxyl groups. In addition to syn dihydroxylation, diols can also be synthesized through the process of anti dihydroxylation. The process involves treating an alkene with a peroxycarboxylic acid to form an epoxide. Epoxides are highly strained three-membered rings with oxygen and two carbons occupying the corners of an equilateral triangle. This step is followed by ring-opening of the epoxide in the presence of an aqueous acid to give a trans diol.
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Catalytic hydrogenation of alkenes is a transition-metal catalyzed reduction of the double bond using molecular hydrogen to give alkanes. The mode of hydrogen addition follows syn stereochemistry.
The metal catalyst used can be either heterogeneous or homogeneous. When hydrogenation of an alkene generates a chiral center, a pair of enantiomeric products is expected to form. However, an enantiomeric excess of one of the products can be facilitated using an enantioselective reaction or an...
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Alkynes to Aldehydes and Ketones: Hydroboration-Oxidation
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.
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Alkynes undergo oxidative cleavage in the presence of oxidizing reagents like potassium permanganate and ozone. The triple bond — one σ bond and two π bonds — is completely cleaved, and the alkyne is oxidized to carboxylic acids. When warm and basic aqueous potassium permanganate is used as an oxidizing agent, alkynes are first converted to carboxylate salts via an unstable α-diketone intermediate. Further, a mild acid treatment protonates the carboxylate anions generating free carboxylic acid...
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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.


