ChemInform Abstract: Highly Selective Electrochemical Fluorination of Dithioacetal Derivatives Bearing Electron-Withdrawing Substituents at the Position α to the Sulfur Atom Using Poly(HF) Salts.

ChemInform ◽  
2015 ◽  
Vol 46 (20) ◽  
pp. no-no
Author(s):  
Bin Yin ◽  
Shinsuke Inagi ◽  
Toshio Fuchigami
Keyword(s):  
Sulfur Atom ◽  
Electrochemical Fluorination ◽  
Electron Withdrawing Substituents

scholarly journals Highly selective electrochemical fluorination of dithioacetal derivatives bearing electron-withdrawing substituents at the position α to the sulfur atom using poly(HF) salts

2015 ◽  
Vol 11 ◽  
pp. 85-91 ◽  
Author(s):  
Bin Yin ◽  
Shinsuke Inagi ◽  
Toshio Fuchigami
Keyword(s):  
Sulfur Atom ◽  
Nitrile Group ◽  
Amide Group ◽  
Sharp Contrast ◽  
Product Selectivity ◽  
Electrochemical Fluorination ◽  
Weak Electron ◽  
Electron Withdrawing Substituents

Anodic fluorination of dithioacetals bearing electron-withdrawing ester, acetyl, amide, and nitrile groups at their α-positions was comparatively studied using various supporting poly(HF) salts like Et3N·nHF (n = 3–5) and Et4NF·nHF (n = 3–5). In the former two cases, the corresponding α-fluorination products or fluorodesulfurization products were obtained selectively depending on supporting poly(HF) salts used. In sharp contrast, in the latter two cases, fluorination product selectivity was strongly affected by the electron-withdrawing ability of α-substituents: A dithioacetal bearing a relatively weak electron-withdrawing amide group provided a fluorodesulfurization product selectively while a dithioacetal having a strongly electron-withdrawing nitrile group gave the α-fluorination product predominantly regardless of the poly(HF) salts used.

Photocatalytic Alkylation of Pyrroles and Indoles with α-Diazo Esters

2019 ◽  
Author(s):  
Łukasz Ciszewski ◽  
Jakub Durka ◽  
Dorota Gryko
Keyword(s):  
Aromatic Compounds ◽  
Reaction Pathway ◽  
Alkylating Agents ◽  
Catalytic Amount ◽  
Radical Formation ◽  
Reaction Selectivity ◽  
Diazo Esters ◽  
Electron Withdrawing Substituents

This article describes direct photoalkylation of electron-rich aromatic compounds with diazo compoiunds. C-2 alkylated indoles and pyrroles are obtained with good yields even though the photocatalyst (Ru(bpy)3Cl2) loading is as low as 0.075 mol %. For substrates bearing electron-withdrawing substituents the addition of a catalytic amount of N,N-dimethyl-4-methoxyaniline is required. Both EWG-EWG and EWG-EDG substituted diazo esters are suitable as alkylating agents. The reaction selectivity and mechanistic experiments suggest that carbenes/carbenoid intermediates are not involved in the reaction pathway, instead radical formation is proposed.

Participation by some oxygen containing groups in hypobromous acid addition to double bond

1983 ◽  
Vol 48 (12) ◽  
pp. 3660-3673 ◽  
Author(s):  
Pavel Kočovský
Keyword(s):  
Double Bond ◽  
Functional Groups ◽  
Relative Reactivity ◽  
Product Analysis ◽  
Acid Addition ◽  
Hypobromous Acid ◽  
Electron Withdrawing Substituents

5(O)n and 6(O)π,n participations by some oxygen containing functional groups in the course of reaction with hypobromous acid have been studied on olefinic models of steroid type (I and II). The ability of these groups to participate has been compared on the basis of their relative reactivity with water (as externally attacking nucleophile) competing with participation. The results of the product analysis show that the ability to react with 5(O)n participation decreases in the order HO > CH3O ≃ CH3OCH2O > CH3CO2 > HCO2 > CH3SO3 ≥ (C2H5O)2PO2 > C6H5CO2 > O2NO ≫ CF3CO2, C2H5OCO2; in the last two functional groups is this ability completely suppressed. The 6(O)π,n participation comes in consideration only for compounds of the type II bearing the groups with the -X=O moiety which are ordered in the following sequence: C2H5OCO2 ≃ CH3CO2 ≥ (C2H5O)2PO2 > HCO2 > C6H5CO2. The remaining functional groups (CF3CO2, O2NO and CH3SO3do not undergo this process. Generally, it is valid that introduction of electron-withdrawing substituents into a participating group impedes or completely suppresses its ability to participate.

Aromaticity in heterocyclic molecules containing divalent sulfur

1988 ◽  
Vol 53 (9) ◽  
pp. 2023-2054 ◽  
Author(s):  
Milan Randić ◽  
Sonja Nikolić ◽  
Nenad Trinajstić
Keyword(s):  
Sulfur Atom ◽  
Positional Isomers ◽  
Heterocyclic Molecules ◽  
Resonance Energies ◽  
Conjugated Circuits ◽  
Divalent Sulfur

The conjugated circuits model is applied to heterocycles containing divalent sulfur. A novel parametrization is introduced for 4n + 2 and 4n conjugated circuits containing a single sulfur atom. The relative aromatic stabilities of a number of heterocyclic systems containing divalent sulfur are studied. Comparison is made whenever possible with earlier reported resonance energies of these compounds, obtained by using Huckel MO and SCF π-MO models, and appropriate reference structures. Special attention is given to positional isomers. An explanation of the differences amongst such isomers is given.

Sulfur Atom Manipulates Geometric Isomerism of Diphosphinine Oxides for Efficient Delayed Fluorescence Diodes

2021 ◽  
pp. 129912
Author(s):  
Fuxing Jiao ◽  
Chengming Zhang ◽  
Guang Lu ◽  
Yi Man ◽  
Chunbo Duan ◽  
...  
Keyword(s):  
Sulfur Atom ◽  
Delayed Fluorescence ◽  
Geometric Isomerism
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