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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.
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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.
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Updated: May 2, 2026

Synthesis of a Borylated Ibuprofen Derivative Through Suzuki Cross-Coupling and Alkene Boracarboxylation Reactions
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La borilación C-H catalizada por el cobalto.

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
Resumen

Los nuevos catalizadores de cobalto realizan eficientemente la borilación C-H de heterociclos y arenas en condiciones suaves. Estos catalizadores muestran una alta actividad, incluso a bajas cargas, sin necesidad de un exceso de reactivos de boro.

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Área de la Ciencia:

  • Química organometálica Química orgánica de los metales.
  • La catálisis de la catálisis.
  • Síntesis orgánica La síntesis orgánica.

Sus antecedentes:

  • La borilación catalítica C-H es crucial para la funcionalización de las moléculas orgánicas.
  • El desarrollo de sistemas catalíticos eficientes y suaves sigue siendo un desafío clave.

Objetivo del estudio:

  • Para sintetizar y evaluar nuevos complejos de cobalto ligado a pinza para la borilación C-H.
  • Investigar la actividad catalítica y las condiciones de reacción para la borilación de heterociclos y arenas.

Principales métodos:

  • Síntesis de complejos de cobalto ligado con pinzas.
  • Pruebas catalíticas para las reacciones de borilación C-H.
  • Optimización de las condiciones de reacción (temperatura, carga del catalizador, reactivos).

Principales resultados:

  • Los complejos de cobalto sintetizados exhiben una alta actividad catalítica para la borilación C-H.
  • Las reacciones se llevan a cabo en condiciones suaves sin requerir un exceso de reactivos de boro.
  • Se lograron altas cifras de rotación (hasta 5000) para metil furan-2-carboxilato a temperatura ambiente con bajas cargas de catalizador (0,02 mol %).

Conclusiones:

  • Los complejos de cobalto ligado con pinza son catalizadores efectivos para la borilación C-H.
  • El sistema catalítico ofrece un enfoque suave, eficiente y de baja carga para la borilación.
  • Se propone un ciclo catalítico que involucra una pareja redox de cobalto (I) - (III) para explicar la reactividad observada.