Asymmetric Enamide–Imine Tautomerism in the Kinetic Resolution of Tertiary Alcohols

Tang, Mingfang; Gu, Huanchao; He, Shunlong; Rajkumar, Subramani; Yang, Xiaoyu

doi:10.1002/ange.202106151

Cited by 6 publications

(1 citation statement)

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“…Numerous cellular processes occur through tautomeric forms of compounds that potentially have tautomerizable groups, and a variety of reactions can be controlled through the displacement of this type of equilibrium. [1][2][3][4][5] Singh et al 6 described that tautomeric nucleoside analogs can act as antiviral drugs due to their ability to induce lethal mutagenesis. After many viruses, such as human immunodeficiency virus (HIV) and COVID-19, infect a cell, they rapidly begin making copies of their genetic material.…”

Section: Introductionmentioning

confidence: 99%

Structural study of some unsaturated malononitriles using mass spectrometry and theoretical models

Garofalo

Gastaca

Albesa

et al. 2023

J of Physical Organic Chem

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The study of tautomerism has gained relevance in the scientific community because several cellular processes occur through different tautomeric forms of certain compounds. The percentage of each tautomer in compounds with tautomerism capability depends on numerous factors, such as temperature and solvent polarity, among others; and, by changing the external conditions, equilibrium displacement can be established very quickly. This manuscript deals with nitrile-ketenimine tautomerism in some unsaturated malononitriles. This kind of compounds with two nitrile groups conjugated to a double bound is able to rearrange accessible hydrogens and provide new and complex structures of different functionalities. The authors' motivation for investigating these compounds lies in understanding their tautomeric behavior in solution and gas phases and to predict reaction deportment to then account for the final products obtained. Four unsaturated malononitriles were synthesized to study the substituent effect on equilibrium displacement. Characterization was performed using nuclear magnetic resonance (NMR) and tautomeric equilibrium in gas phase was evaluated by mass spectrometry. Correlation with theoretical calculations was carried out in order to comprehend the system behavior.

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Section: Introductionmentioning

confidence: 99%

Structural study of some unsaturated malononitriles using mass spectrometry and theoretical models

Garofalo

Gastaca

Albesa

et al. 2023

J of Physical Organic Chem

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Brønsted Acid Catalyzed Dearomatization by Intramolecular Hydroalkoxylation/Claisen Rearrangement: Diastereo‐ and Enantioselective Synthesis of Spirolactams

Chen

Zhou

et al. 2021

Angewandte Chemie

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Described herein is a novel Brønsted acid catalyzed intramolecular hydroalkoxylation/Claisen rearrangement, allowing the practical and atom‐economic synthesis of a range of valuable spirolactams from readily available ynamides in generally good to excellent yields with excellent diastereoselectivities and broad substrate scope. Importantly, an unexpected dearomatization of nonactivated arenes and heteroaromatic compounds is involved in this tandem sequence. Moreover, an asymmetric version of this tandem cyclization was also achieved by efficient kinetic resolution by chiral phosphoric acid catalysis. In addition, the [3,3]‐rearrangement is shown to be kinetically preferred over the related [1,3]‐rearrangement by theoretical calculations.

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Synthesis of W‐Phos Ligand and Its Application in the Copper‐Catalyzed Enantioselective Addition of Linear Grignard Reagents to Ketones

et al. 2022

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The asymmetric catalytic addition of linear Grignard reagents to ketones has been a long-standing challenge in organic synthesis. Herein, a novel family of PNP ligands (W-Phos) was designed and applied in copper-catalyzed asymmetric addition of linear Grignard reagents to aryl alkyl ketones, allowing facile access to versatile chiral tertiary alcohols in good to high yields with excellent enantioselectivities (up to 94 % yield, 96 % ee). The process can also be used to synthesize chiral allylic tertiary alcohols from more challenging α,βunsaturated ketones. Notably, the potential utility of this method is demonstrated in the gram-scale synthesis and modification of various densely functionalized medicinally relevant molecules.

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Asymmetric Enamide–Imine Tautomerism in the Kinetic Resolution of Tertiary Alcohols

Cited by 6 publications

References 99 publications

Structural study of some unsaturated malononitriles using mass spectrometry and theoretical models

Structural study of some unsaturated malononitriles using mass spectrometry and theoretical models

Brønsted Acid Catalyzed Dearomatization by Intramolecular Hydroalkoxylation/Claisen Rearrangement: Diastereo‐ and Enantioselective Synthesis of Spirolactams

Synthesis of W‐Phos Ligand and Its Application in the Copper‐Catalyzed Enantioselective Addition of Linear Grignard Reagents to Ketones

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