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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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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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双原子催化用于交叉合

Xiao Hai1, Yang Zheng1, Qi Yu2,3

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

Nature
|September 21, 2023
PubMed
概括
此摘要是机器生成的。

双原子催化剂 (GAC) 为增强有机合成配对单个原子. 这些新型催化剂可实现高效的C-X交叉合和复杂分子组合,克服单原子催化剂的局限性.

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科学领域:

  • 不同质的催化
  • 材料科学
  • 有机合成

背景情况:

  • 单原子催化剂 (SAC) 提供了明确的活性位点,但由于受限的环境,复杂的转化具有局限性.
  • 在SAC中单核金属物种的空间排列和电子状态可能会阻碍最佳的催化活性.

研究的目的:

  • 引入一种新型的异质双原子催化剂 (GAC),使单原子位点相邻.
  • 证明GAC在各种C-X交叉合反应中的增强催化性能.

主要方法:

  • 使用聚合碳化物 (PCN) 主体与固定组进行Cu协调的GAC合成.
  • 在现场表征和量子理论研究以阐明反应机制.
  • 在各种C-X (X=C,N,O,S) 交叉合反应中测试GAC.

主要成果:

  • 在高金属密度下,GAC 呈现出 Cu 原子的特定协调和空间近距离 (~4 Å 分离).
  • 一个由动态Cu-Cu结合促进的合作桥接通道使低激活障碍的交叉合成为可能.
  • 在合成复杂的异环,固态阻碍分子和药物方面,GACs具有很高的活性和选择性.

结论:

  • 双原子催化剂在复杂的有机合成中比SACs具有显著的进步.
  • 在GAC中独特的合作机制可以防止同质合,并促进多种交叉合反应.
  • 在精细化工制造业中,GAC具有广泛的适用性,包括扩大规模和连续流程.