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Spin–Spin Coupling: Two-Bond Coupling (Geminal Coupling)01:20

Spin–Spin Coupling: Two-Bond Coupling (Geminal Coupling)

1.1K
Two NMR-active nuclei bonded to a central atom can be involved in geminal or two-bond coupling. Geminal coupling is commonly seen between diastereotopic protons in chiral molecules and unsymmetrical alkenes, among others.
The central atom need not be NMR-active because its electrons are affected by the electron polarization of the spin-active atoms. However, spin information is transmitted less effectively than in one-bond coupling, and 2J values are usually weaker than 1J values. The energy of...
1.1K
Crossed Aldol Reactions: Overview01:04

Crossed Aldol Reactions: Overview

5.4K
Crossed aldol addition is the reaction between two different carbonyl compounds under acidic or basic conditions. Here, both the carbonyl compounds function as nucleophiles and electrophiles. As shown in Figure 1, such a reaction yields a mixture of products, two of which are formed via self-condensation, while the remaining two are formed via crossed-condensation. Without adjustment, the reaction's usefulness in organic chemistry is decreased.
5.4K
Reduction of Alkynes to cis-Alkenes: Catalytic Hydrogenation02:24

Reduction of Alkynes to cis-Alkenes: Catalytic Hydrogenation

7.8K
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.
7.8K
Alkenes via Reductive Coupling of Aldehydes or Ketones: McMurry Reaction01:22

Alkenes via Reductive Coupling of Aldehydes or Ketones: McMurry Reaction

1.9K
The radical dimerization of ketones or aldehydes gives vicinal diols through a pinacol coupling reaction. However, the behavior of titanium metals used for the reaction as a source of electrons is unusual. When the reaction is carried out in the presence of titanium, diols can be isolated at low temperatures. Else titanium further reacts with diols, forming alkenes through the McMurry reaction.
1.9K
β-Dicarbonyl Compounds via Crossed Claisen Condensations01:18

β-Dicarbonyl Compounds via Crossed Claisen Condensations

3.1K
Crossed Claisen condensations are base-promoted reactions between two different ester molecules producing β-dicarbonyl compounds.  The reaction involving esters, with both containing α hydrogen, results in a mixture of four different products that are difficult to isolate. This reduces the synthetic utility of the reaction.
3.1K
Reduction of Alkenes: Asymmetric Catalytic Hydrogenation02:17

Reduction of Alkenes: Asymmetric Catalytic Hydrogenation

3.3K
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...
3.3K

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Video Experimental Relacionado

Updated: Jul 16, 2025

Mizoroki-Heck Cross-coupling Reactions Catalyzed by Dichloro{bis[1,1',1''-phosphinetriyltripiperidine]}palladium Under Mild Reaction Conditions
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Mizoroki-Heck Cross-coupling Reactions Catalyzed by Dichloro{bis[1,1',1''-phosphinetriyltripiperidine]}palladium Under Mild Reaction Conditions

Published on: March 20, 2014

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Catálisis de átomos geminales para el acoplamiento cruzado

Xiao Hai1, Yang Zheng1, Qi Yu2,3

  • 1Department of Chemistry, National University of Singapore, Singapore, Singapore.

Nature
|September 21, 2023
PubMed
Resumen
Este resumen es generado por máquina.

Los catalizadores de átomos geminales (GAC) emparejan átomos individuales para mejorar la síntesis orgánica. Estos nuevos catalizadores permiten acoplamientos cruzados C-X eficientes y ensamblaje de moléculas complejas, superando las limitaciones de los catalizadores de un solo átomo.

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Área de la Ciencia:

  • Catálisis heterogénea
  • Ciencias de los materiales
  • Síntesis orgánica

Sus antecedentes:

  • Los catalizadores de un solo átomo (SAC) ofrecen sitios activos bien definidos, pero tienen limitaciones en las transformaciones complejas debido a entornos restringidos.
  • La disposición espacial y los estados electrónicos de las especies de metales mononucleares en los SAC pueden obstaculizar la actividad catalítica óptima.

Objetivo del estudio:

  • Introducir una nueva clase de catalizadores de átomos geminales heterogéneos (GAC) que emparejen sitios de un solo átomo en las proximidades.
  • Demostrar el rendimiento catalítico mejorado de los GAC para diversas reacciones de acoplamiento cruzado C-X.

Principales métodos:

  • Síntesis de GAC utilizando un anfitrión polimérico de nitruro de carbono (PCN) con grupos de anclaje de nitrógeno para la coordinación de Cu.
  • Caracterización in situ y estudios teóricos cuánticos para elucidar los mecanismos de reacción.
  • Prueba de los GAC en varias reacciones de acoplamiento cruzado C-X (X = C, N, O, S).

Principales resultados:

  • Los GAC exhiben una coordinación específica y proximidad espacial de los átomos de Cu (separación de ~ 4 Å) a alta densidad de metal.
  • Una vía de acoplamiento de puente cooperativa facilitada por la unión dinámica Cu-Cu permite acoplamientos cruzados eficientes con bajas barreras de activación.
  • Los GAC demuestran una alta actividad y selectividad en la síntesis de heterociclos complejos, moléculas estéricamente obstaculizadas y productos farmacéuticos.

Conclusiones:

  • Los catalizadores de átomos geminales representan un avance significativo con respecto a los SAC para la síntesis orgánica compleja.
  • El mecanismo cooperativo único en los GAC previene el homoacoplamiento y promueve diversas reacciones de acoplamiento cruzado.
  • Los GAC muestran una amplia aplicabilidad para la fabricación de productos químicos finos, incluidos los procesos a escala y de flujo continuo.