Recent progress in the asymmetric Mannich reaction

Cai, Xiaohua; Guo, Hui; Xie, Bing

doi:10.5155/eurjchem.3.2.258-266.536

Cited by 35 publications

(6 citation statements)

References 58 publications

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“…The asymmetric 1,2-addition of various nucleophiles to imines represents a very important class of reactions for providing chiral amine derivatives . However, enantioselective organocatalytic 1,2-additions of sulfur nucleophiles to imines were not reported until 2011, when Antilla’s group published a catalytic asymmetric 1,2-addition of thiols to imines (Scheme ) .…”

Section: Enantioselective Organocatalytic C–s Bond Formationsmentioning

confidence: 99%

Organocatalytic Carbon–Sulfur Bond-Forming Reactions

2014

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Section: Enantioselective Organocatalytic C–s Bond Formationsmentioning

confidence: 99%

Organocatalytic Carbon–Sulfur Bond-Forming Reactions

2014

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“…Recent developments on asymmetric Mannich reactions include asymmetric catalysis using enantiopure scandium(III), 6,7 copper, 8,9 and palladium complexes. 10 Nevertheless, the majority of Mannich reactions are still based on enamine catalysis and new examples keep emerging, thereby continuously increasing the scope.…”

Section: Introductionmentioning

confidence: 99%

Efficient catalysts for asymmetric Mannich reactions

et al. 2013

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Efficient chiral catalysts for direct asymmetric three-component Mannich reactions of ketones, aldehydes and an amine (p-anisidine) have been developed. The corresponding β-amino carbonyl compounds (Mannich adducts) were obtained in good chemical yields and excellent enantio- and diastereoselectivities. The reaction conditions have been optimized by invoking ultrasonication and the influence of some structural moieties of the catalysts on the chemical yield and stereoselectivity of the Mannich products has been evaluated.

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“…As imine electrophiles and carbonyl nucleophiles are amenable to a variety of catalytic modes of activation, we identified the organocatalytic Mannich reaction as the unifying reaction platform (Figure 3A). [23][24][25][26] This reaction type provides a wide range of both substrate and catalyst structures from published sources. We curated a dataset consisting of 3003 reactions from 106 publications wherein diverse chiral H-bonding (1418 reactions), Brønsted acid (256 reactions), covalent catalysts (1182 reactions), and miscellaneous catalysts (147 reactions) had been employed (Figure 3).…”

Section: Resultsmentioning

confidence: 99%

An Unsupervised Machine Learning Workflow for Assigning and Predicting Generality in Asymmetric Catalysis

Betinol

Lai

Thakur

et al. 2023

Preprint

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The development of chiral catalysts that can provide high enantioselectivities across a wide assortment of substrates or reaction range is a priority for many catalyst design efforts. While several approaches are available to aid in the identification of general catalyst systems there is currently no simple procedure for directly measuring how general a given catalyst could be. Herein, we present a catalyst-agnostic workflow centered on unsupervised machine learning that enables the rapid assessment and quantification of catalyst generality. The workflow uses curated literature data sets and reaction descriptors to visualize and cluster chemical space coverage. This reaction network can then be applied to derive a catalyst generality metric through designer equations and interfaced with other regression techniques for general catalyst prediction. As validating case studies, we have successfully applied this method to identi-fy-through-quantification the most general catalyst chemotype for an organocatalytic asymmetric Mannich reaction and predicted the most general chiral phosphoric acid catalyst for the addition of nucleophiles to imines. The mechanistic basis for catalyst generality can then be gleaned from the calculated values by deconstructing the contributions of chemical space and enantiomeric excess to the overall result. We conclude that broadly applicable catalysts may be more adaptative to changes in reactant structure because enantioinduction does not rely on a single set of noncovalent interactions. In contrast, some systems work by engaging in robust noncovalent contacts that do not change significantly in nature when the structure of the reaction component is altered. Finally, our generality techniques permit-ted the development of mechanistically informative catalyst screening sets that allow experimentalists to rationally select catalysts that have the highest probability of achieving a good result in the first round of reaction development. Overall, our findings represent a framework for interrogating and predicting catalyst generality, and this strategy should be relevant to other catalytic systems widely applied in asymmetric synthesis.

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Recent progress in the asymmetric Mannich reaction

Cited by 35 publications

References 58 publications

Organocatalytic Carbon–Sulfur Bond-Forming Reactions

Organocatalytic Carbon–Sulfur Bond-Forming Reactions

Efficient catalysts for asymmetric Mannich reactions

An Unsupervised Machine Learning Workflow for Assigning and Predicting Generality in Asymmetric Catalysis

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