Thiophene Substitution Chemistry

Ryabova, Victoria; Игнатович, Л.

doi:10.1007/7081_2014_134

Cited by 10 publications

(4 citation statements)

References 184 publications

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“…Conversely, weak affinities are predicted for diethylsulfide and tetrahydrothiophene (Table ), certainly because of the inability of these saturated ligands to stabilize a positive charge by the mesomeric effect. The interaction of AtO + with thiophene was also investigated in order to confirm, in thiophene derivatives, the preferred nucleophilic site in α-position of the sulfur atom, resulting in a O–C bond formation (Figure ).…”

Section: Discussionmentioning

confidence: 99%

Questioning the Affinity of Electrophilic Astatine for Sulfur-containing Compounds: Unexpected Bindings Revealed

et al. 2020

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The affinity of AtO + for around 20 model ligands (L), carrying functionalized oxygen, sulfur, and nitrogen atoms, has been assessed through a combined experimental and theoretical methodology. Significant equilibrium constants (K L ∼ 10 4 ) have been measured for sulfur-containing compounds, in agreement with the previously highlighted, relatively stable radiolabeling of SH-containing proteins with 211 At. Conversely, no interaction occurs in the aqueous phase for their oxygenated counterparts, but higher affinities (K L > 10 6 ) have been determined for nitrogen-based ligands, including aromatic nitrogen heterocycles. The quantum mechanical calculations definitively ruled out any rationale based on either the metallic character of astatine or its guessed softness; the favored interactions all involve specifically the oxygen atom of AtO + , leading to the formation of covalent O−S or O−C single bonds.

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Section: Discussionmentioning

confidence: 99%

Questioning the Affinity of Electrophilic Astatine for Sulfur-containing Compounds: Unexpected Bindings Revealed

et al. 2020

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“…64 Rule 4 states that reactants with active hydrogen atoms have an adverse effect on CuAAC reaction due to a copper electrophilic substitution reaction. 65,66 Rule 5 states that reactants with carbonyl groups have adverse effects on CuAAC reactions due to allenation of terminal alkynes with ketones. 67 Based on the above-mentioned analyses, we hypothesized that related quantitative descriptors can be more appropriate for reaction predictions.…”

Section: ■ Discussionmentioning

confidence: 99%

“…Rule 3 states that aromatic bromides have adverse effects on CuAAC reactions due to the side reaction: the Castro–Stephens reaction . Rule 4 states that reactants with active hydrogen atoms have an adverse effect on CuAAC reaction due to a copper electrophilic substitution reaction. , Rule 5 states that reactants with carbonyl groups have adverse effects on CuAAC reactions due to allenation of terminal alkynes with ketones …”

Section: Discussionmentioning

confidence: 99%

Predicting the Feasibility of Copper(I)-Catalyzed Alkyne–Azide Cycloaddition Reactions Using a Recurrent Neural Network with a Self-Attention Mechanism

Yang

Gan

et al. 2020

J. Chem. Inf. Model.

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The copper(I)-catalyzed alkyne–azide cycloaddition (CuAAC) reaction, a major click chemistry reaction, is widely employed in drug discovery and chemical biology. However, the success rate of the CuAAC reaction is not satisfactory as expected, and in order to improve its performance, we developed a recurrent neural network (RNN) model to predict its feasibility. First, we designed and synthesized a structurally diverse library of 700 compounds with the CuAAC reaction to obtain experimental data. Then, using reaction SMILES as input, we generated a bidirectional long–short-term memory with a self-attention mechanism (BiLSTM-SA) model. Our best prediction model has total accuracy of 80%. With the self-attention mechanism, adverse substructures responsible for negative reactions were recognized and derived as quantitative descriptors. Density functional theory investigations were conducted to provide evidence for the correlation between bromo-α-C hybrid types and the success rate of the reaction. Quantitative descriptors combined with RDKit descriptors were fed to three machine learning models, a support vector machine, random forest, and logistic regression, and resulted in improved performance. The BiLSTM-SA model for predicting the feasibility of the CuAAC reaction is superior to other conventional learning methods and advances heuristic chemical rules.

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“…In this work, we demonstrate a facile approach to new AIEgens bearing a thieno-fused phosphole oxide ( TPO ) unit as a stator framework via a one-pot synthesis. Selective chemical modifications are much more straightforward on thiophene derivatives , than corresponding phenyl derivatives, making them ideal precursor compounds for the smart design of novel optically active materials. In addition to the specifics of the synthesis, we also investigated the substituent effect at the thiophene moiety on the photophysical properties.…”

Section: Introductionmentioning

confidence: 99%

Access to Strong Thieno[3,2-b]phosphole-Based Solid-State Emitters via Manganese(III)-Mediated Oxidative Annulation

König,

Godínez-Loyola,

Weiske

et al. 2023

Chem. Mater.

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The synthesis of novel organic molecular frameworks with strong luminescence in the solid state has become an enormously growing area of current research due to their versatile applications for optoelectronics or bioimaging. Here, a facile synthetic strategy via Mn III -mediated oxidative annulation reaction to obtain propeller-rich molecules bearing a thieno[3,2-b]phosphole motif as a stator moiety is reported. All synthesized compounds show aggregation-induced emission (AIE) characteristics, strong fluorescence in the solid state, and substituentdependency of the photophysical properties. The phosphinated thieno[3,2-b]phospholes possess a high degree of restrictions on intramolecular motions, leading to powerful solid-state light emitters with fluorescence quantum yields close to 100% and lifetimes up to 7.9 ns, even at room temperature.

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Thiophene Substitution Chemistry

Cited by 10 publications

References 184 publications

Questioning the Affinity of Electrophilic Astatine for Sulfur-containing Compounds: Unexpected Bindings Revealed

Questioning the Affinity of Electrophilic Astatine for Sulfur-containing Compounds: Unexpected Bindings Revealed

Predicting the Feasibility of Copper(I)-Catalyzed Alkyne–Azide Cycloaddition Reactions Using a Recurrent Neural Network with a Self-Attention Mechanism

Access to Strong Thieno[3,2-b]phosphole-Based Solid-State Emitters via Manganese(III)-Mediated Oxidative Annulation

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