Advances in Mannich‐type Reactions Based on the Classification of Compounds with Activated α‐H

Lv, Haining; Du, Yipeng; Zhang, Haibin; Zheng, Yuxin; Yan, Zhijia; Dong, Ning

doi:10.1002/slct.202300173

Cited by 4 publications

(1 citation statement)

References 68 publications

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“…In this case, alternative α-amino acid precursors bearing ester or furane units instead of the cyano group may be helpful. Such precursors can be enantioselectively prepared from glyoxylate imines or furfural imines by means of the asymmetric Mannich reaction with enolizable carbonyl compounds in the presence of chiral transition metal complexes or metal-free organocatalysts, preferably chiral amines . Since the breakthrough discovery of List, the organocatalytic Mannich reaction has been recognized as an important methodology for the enantioselective construction of a carbon–carbon bond to build various chiral β-amino carbonyl moieties .…”

Section: Introductionmentioning

confidence: 99%

Asymmetric Synthesis of Functionalized α-Amino Acid Derivatives via the γ-Pyrone Carbaldimine-Based Organocatalytic Mannich Reaction

Smirnov,

Zhanabaeva,

Kucherenko

et al. 2024

J. Org. Chem.

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A powerful synthetic strategy for the asymmetric synthesis of enantiomerically enriched γ-functionalized α-amino acid derivatives based on the highly stereoselective prolinecatalyzed Mannich-type reaction of pre-prepared or in situgenerated γ-pyrone-derived aldimines with carbonyl compounds and subsequent transformations of multifunctional reaction products has been developed. A significant positive nonlinear effect was detected for the key organocatalytic reaction. The developed strategy was applied for facile gram-scale preparation of (S)-γ-oxonorvaline, used for site-specific modification of proteins, and both enantiomers of amycolatolide A recently isolated from the lichen-derived actinomycete Amycolatopsis sp. YIM 130923.

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Section: Introductionmentioning

confidence: 99%

Asymmetric Synthesis of Functionalized α-Amino Acid Derivatives via the γ-Pyrone Carbaldimine-Based Organocatalytic Mannich Reaction

Smirnov,

Zhanabaeva,

Kucherenko

et al. 2024

J. Org. Chem.

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Unraveling the Push‐Pull Effect in Acenes, Polyenes and Polyynes

Wieczorkiewicz,

Shahamirian,

Kupka

et al. 2023

Chemistry A European J

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Substituent effects (SEs) are fundamental for predicting molecular reactivity, while polyene, polyyne and acene derivatives are precursors to compounds with diverse applications. Computations were performed for Y‐R‐X systems, where reaction sites Y = NO2 and O−, substituents X = NO2, CN, Cl, H, OH, NH2, and spacers R = polyene, polyyne (n=1‐5, 10 repeating units) and acene (up to tetracene). The cSAR (charge of the substituent active region) approach allowed to present, for the first time, quantitative relations describing the spacer’s electron‐donating and withdrawing properties as a function of n and the spacer type. The electronic properties of the X substituents depend on the type of spacer, its length and the Y group, which is an example of the reverse SE. To describe how the SE between Y and X weakens with n, two approaches were compared: cSAR and SESE (SE stabilization energy). The EDDB (electron density of delocalized bonds) characterize changes in electron delocalization in spacers due to the SE. A new approach – EDDB differential maps – allow to extract the effect of X substitution on the electron delocalization. The charges at spacer’s C atoms correlate with cSAR; changes in the slopes confirm the charge transfer by resonance.

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Organocatalysis for Enantioselective Decarboxylative Nucleophilic Addition Reactions

Yasukawa,

Nakamura

2024

Eur J Org Chem

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The catalytic decarboxylation of malonic acid half oxy‐ and thioesters, β‐ketocarboxylic acids, and their related compounds is a straightforward, powerful, and atom‐economical strategy for the in‐situ formation of enolates, which are important and well‐studied synthons for various functional materials and natural products. This strategy, inspired by the biosynthesis of polyketides and fatty acids, is an attractive method for synthesizing enols from carboxyl compounds with less reactive α‐hydrogen atoms under mild conditions. In addition, these reactions are environmentally friendly and are of great interest to chemists because the use of a stoichiometric amount of base can be avoided, and the only byproduct is CO2. Thus far, remarkable progress has been made, especially in the field of organocatalytic enantioselective decarboxylation reactions, allowing for the stereocontrolled formation of new C–H, C–C, C–heteroatom, and C–X bonds. This review provides a comprehensive overview of organocatalytic enantioselective decarboxylation reactions and highlights the significant progress made since 2020. In particular, it focuses on chiral catalyst systems and transition states as key parameters for decarboxylation reactions.

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Advances in Mannich‐type Reactions Based on the Classification of Compounds with Activated α‐H

Cited by 4 publications

References 68 publications

Asymmetric Synthesis of Functionalized α-Amino Acid Derivatives via the γ-Pyrone Carbaldimine-Based Organocatalytic Mannich Reaction

Asymmetric Synthesis of Functionalized α-Amino Acid Derivatives via the γ-Pyrone Carbaldimine-Based Organocatalytic Mannich Reaction

Unraveling the Push‐Pull Effect in Acenes, Polyenes and Polyynes

Organocatalysis for Enantioselective Decarboxylative Nucleophilic Addition Reactions

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