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Regioselectivity and Stereochemistry of Hydroboration02:36

Regioselectivity and Stereochemistry of Hydroboration

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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...
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Alkynes to Aldehydes and Ketones: Hydroboration-Oxidation02:47

Alkynes to Aldehydes and Ketones: Hydroboration-Oxidation

19.8K
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.
19.8K
Hydroboration-Oxidation of Alkenes03:08

Hydroboration-Oxidation of Alkenes

10.1K
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.
10.1K
Acid-Catalyzed α-Halogenation of Aldehydes and Ketones01:21

Acid-Catalyzed α-Halogenation of Aldehydes and Ketones

3.1K
By replacing an α-hydrogen with a halogen, acid-catalyzed α-halogenation of aldehydes or ketones yields a monohalogenated product
In the first step of the mechanism, the acid protonates the carbonyl oxygen resulting in a resonance-stabilized cation, which subsequently loses an α-hydrogen to form an enol tautomer. The C=C bond in an enol is highly nucleophilic because of the electron-donating nature of the –OH group. Consequently, the double bond attacks an electrophilic...
3.1K
Reduction of Alkynes to cis-Alkenes: Catalytic Hydrogenation02:24

Reduction of Alkynes to cis-Alkenes: Catalytic Hydrogenation

6.9K
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.
6.9K
Halogenation of Alkenes02:46

Halogenation of Alkenes

17.1K
Halogenation is the addition of chlorine or bromine across the double bond in an alkene to yield a vicinal dihalide. The reaction occurs in the presence of inert and non-nucleophilic solvents, such as methylene chloride, chloroform, or carbon tetrachloride.
Consider the bromination of cyclopentene. Molecular bromine is polarized in the proximity of the π electrons of cyclopentene. An electrophilic bromine atom adds across the double bond, forming a cyclic bromonium ion intermediate.
17.1K

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相关实验视频

Updated: May 2, 2026

Synthesis of a Borylated Ibuprofen Derivative Through Suzuki Cross-Coupling and Alkene Boracarboxylation Reactions
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Synthesis of a Borylated Ibuprofen Derivative Through Suzuki Cross-Coupling and Alkene Boracarboxylation Reactions

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用催化的C-H玻利化

Jennifer V Obligacion1, Scott P Semproni, Paul J Chirik

  • 1Department of Chemistry, Princeton University , Princeton, New Jersey 08544, United States.

Journal of the American Chemical Society
|March 5, 2014
PubMed
概括

新的催化剂在温和条件下高效地执行异环和的C-H化. 这些催化剂表现出高活性,即使在低负载下,也不需要多余的试剂.

科学领域:

  • 有机金属化学 有机金属化学
  • 催化剂是一种催化剂.
  • 有机合成 有机合成

背景情况:

  • 催化C-H玻利化对于有机分子的功能化至关重要.
  • 开发高效和温和的催化系统仍然是一个关键的挑战.

研究的目的:

  • 合成和评估用于C-H玻利化的新型结合复合物.
  • 为了研究催化活性和反应条件,用于 heterocycles 和 arenes 的化.

主要方法:

  • 合合金复合物的合成.
  • 对C-H玻利化反应进行催化试验.
  • 反应条件的优化 (温度,催化剂负载,试剂).

主要成果:

  • 合成的复合体对C-H玻利化具有很高的催化活性.
  • 反应在温和的条件下进行,不需要多余的试剂.
  • 在环境温度下与低催化剂负载 (0.02 mol %) 的甲基 furan-2-carboxylate 实现了高周转率 (高达 5000).

结论:

  • 结合的合金复合物是C-H化过程的有效催化剂.

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  • 催化系统提供了一种温和,高效和低负载的化方法.
  • 建议使用一种涉及 (I) - (III) 氧化还原对的催化循环来解释观察到的反应性.