General Methods for the Preparation of Enolates

Braun, Manfred

doi:10.1002/9783527671069.ch2

Modern Enolate Chemistry 2015

DOI: 10.1002/9783527671069.ch2

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General Methods for the Preparation of Enolates

Manfred Braun

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Cited by 3 publications

References 290 publications

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Destabilized Carbocations Caged in Water Microdroplets: Isolation and Real-Time Detection of α-Carbonyl Cation Intermediates

et al. 2022

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Over the last 50 years, proposals of α-carbonyl cation intermediates have been driven by chemical intuition and indirect evidence. Recently, wide interest in α-carbonyl cation chemistry has opened new gates to prepare α-functionalized carbonyl compounds. Though these intrinsically unstable carbocations are formed under forcing conditions (e.g., in a strong acid medium), their fleeting existence prohibits direct observation or spectroscopic measurement. We report that high-speed aqueous microdroplets can directly capture α-carbonyl cation intermediates from various reactions (Friedel−Crafts arylation, deoxygenation, and azidation) upon bombarding with the corresponding reaction aliquots. The α-carbonyl cations caged in water droplets are then desorbed to the gas phase, allowing their successful measurement by mass spectrometry. This has also enabled us to simultaneously monitor the relative abundance of the associated precursor, α-carbonyl cation intermediate, and product during the progress of the reaction.

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Destabilized Carbocations Caged in Water Microdroplets: Isolation and Real-Time Detection of α-Carbonyl Cation Intermediates

et al. 2022

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A Coupling Approach for the Generation of α,α-Bis(enolate) Equivalents: Regioselective Synthesis of gem-Difunctionalized Ketones

et al. 2018

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Regioselective α,α-difunctionalization adjacent to a ketone is a significant synthetic challenge. Here, we present a solution to this problem through the transition-metal-free coupling of esters with geminal bis(boron) compounds. This forms an α,α-bis(enolate) equivalent which can be trapped with electrophiles including alkyl halides and fluorinating agents. This presents an efficient, convergent synthetic strategy for the synthesis of unsymmetrical blocked ketones.

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Rapid and Accurate Prediction of pK_a Values of C–H Acids Using Graph Convolutional Neural Networks

et al. 2019

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The ability to estimate the acidity of C−H groups within organic molecules in non-aqueous solvents is important in synthetic planning to correctly predict which protons will be abstracted in reactions such as alkylations, Michael additions, or aldol condensations. This Article describes the use of the socalled graph convolutional neural networks (GCNNs) to perform such predictions on the time scales of milliseconds and with accuracy comparing favorably with state-of-the-art solutions, including commercial ones. The crux of the method is to train GCNNs using descriptors that reflect not only topological but also chemical properties of atomic environments. The model is validated against adversarial controls, supplemented by the discussion of realistic synthetic problems (on which it correctly predicts the most acidic protons in >90% of cases), and accompanied by a Web application intended to aid the community in everyday synthetic planning.

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General Methods for the Preparation of Enolates

Cited by 3 publications

References 290 publications

Destabilized Carbocations Caged in Water Microdroplets: Isolation and Real-Time Detection of α-Carbonyl Cation Intermediates

Destabilized Carbocations Caged in Water Microdroplets: Isolation and Real-Time Detection of α-Carbonyl Cation Intermediates

A Coupling Approach for the Generation of α,α-Bis(enolate) Equivalents: Regioselective Synthesis of gem-Difunctionalized Ketones

Rapid and Accurate Prediction of pK_a Values of C–H Acids Using Graph Convolutional Neural Networks

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General Methods for the Preparation of Enolates

Cited by 3 publications

References 290 publications

Destabilized Carbocations Caged in Water Microdroplets: Isolation and Real-Time Detection of α-Carbonyl Cation Intermediates

Destabilized Carbocations Caged in Water Microdroplets: Isolation and Real-Time Detection of α-Carbonyl Cation Intermediates

A Coupling Approach for the Generation of α,α-Bis(enolate) Equivalents: Regioselective Synthesis of gem-Difunctionalized Ketones

Rapid and Accurate Prediction of pKa Values of C–H Acids Using Graph Convolutional Neural Networks

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Product

Resources

About

Rapid and Accurate Prediction of pK_a Values of C–H Acids Using Graph Convolutional Neural Networks