Making Chiral Salen Complexes Work with Organocatalysts.
Yu-Chao Yuan1,2, Mohamed Mellah1, Emmanuelle Schulz1
1Université Paris-Saclay, CNRS, Institut de Chimie Moléculaire et des Matériaux d'Orsay, 91405 Orsay, France.
Chemical Reviews
|March 10, 2022
Summary
Chiral salens ligands enhance asymmetric catalysis when combined with organocatalysts. This review classifies and analyzes these cooperative catalytic systems, detailing their mechanisms.
Area of Science:
- Coordination Chemistry
- Asymmetric Catalysis
- Organocatalysis
Background:
- Salen ligands derived from salicylaldehyde and chiral diamines are crucial in asymmetric organometallic catalysis.
- These ligands can cooperate with organocatalysts, acting as additives to modify metal reactivity or as true co-catalysts.
Purpose of the Study:
- To review and classify literature scenarios of salen ligands cooperating with organocatalysts.
- To elucidate the mechanistic and physical-organic chemistry principles governing these complex catalytic systems.
Main Methods:
- Literature review and classification based on the type of organocatalyst.
- Analysis of mechanistic pathways and physical-organic chemistry principles.
Main Results:
- Identification and categorization of various cooperative modes between salen ligands and organocatalysts.
- Detailed mechanistic insights into how organocatalysts influence metal-ligand complexes.
Conclusions:
- Cooperative catalysis involving chiral salen ligands and organocatalysts offers versatile strategies for asymmetric synthesis.
- Understanding the mechanistic interplay is key to designing efficient and selective catalytic systems.
More Related Videos
Related Concept Videos
Reduction of Alkenes: Asymmetric Catalytic Hydrogenation
3.5K
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...
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...
3.5K
Prochirality
4.1K
The concept of prochirality leads to the nomenclature of the individual faces of a molecule and plays a crucial role in the enantioselective reaction. It is a concept where two or more achiral molecules react to produce chiral products. A typical process is the reaction of an achiral ketone to generate a chiral alcohol. Here, the achiral reactant reacts with an achiral reducing agent, sodium borohydride, to generate an equimolar mixture of the chiral enantiomers of the product. For example, an...
4.1K
Radical Halogenation: Stereochemistry
3.9K
Stereochemistry is the study of the different spatial arrangements of atoms in a given molecule. The stereochemistry of radical halogenations can be understood from three different situations:
Halogenation to form a new chiral center:
Halogenation to form a new chiral center:
3.9K
SN2 Reaction: Stereochemistry
10.0K
In an SN2 reaction, the nucleophilic attack on the substrate and departure of the leaving group occurs simultaneously through a transition state. As the nucleophile approaches the substrate from the back-side, the configuration of the substrate carbon changes from tetrahedral to trigonal bipyramidal and then back to tetrahedral, leading to an inversion in the configuration of the product.
If the substrate is an achiral molecule at the α-carbon, the inversion of configuration is not...
If the substrate is an achiral molecule at the α-carbon, the inversion of configuration is not...
10.0K
Chirality at Nitrogen, Phosphorus, and Sulfur
6.1K
Chirality is most prevalent in carbon-based tetrahedral compounds, but this important facet of molecular symmetry extends to sp3-hybridized nitrogen, phosphorus and sulfur centers, including trivalent molecules with lone pairs. Here, the lone pair behaves as a functional group in addition to the other three substituents to form an analogous tetrahedral center that can be chiral.
A consequence of chirality is the need for enantiomeric resolution. While this is theoretically possible for all...
A consequence of chirality is the need for enantiomeric resolution. While this is theoretically possible for all...
6.1K
Regioselectivity and Stereochemistry of Acid-Catalyzed Hydration
8.7K
The rate of acid-catalyzed hydration of alkenes depends on the alkene's structure, as the presence of alkyl substituents at the double bond can significantly influence the rate.
8.7K


