Reactions of aryl diazonium salts and arylazo alkyl ethers in basic alcoholic solvents. Steric and mechanistic studies

1977 ◽  
Vol 42 (14) ◽  
pp. 2454-2458 ◽  
Author(s):  
Christopher S. Anderson ◽  
Trevor J. Broxton
Keyword(s):  
Diazonium Salts ◽  
Mechanistic Studies ◽  
Alkyl Ethers

Boron insertion into alkyl ether bonds via zinc/nickel tandem catalysis

Science ◽  
2021 ◽  
Vol 372 (6538) ◽  
pp. 175-182
Author(s):  
Hairong Lyu ◽  
Ilia Kevlishvili ◽  
Xuan Yu ◽  
Peng Liu ◽  
Guangbin Dong
Keyword(s):  
Nickel Catalyst ◽  
Bioactive Compounds ◽  
Cyclic Ethers ◽  
Alkyl Ether ◽  
Tandem Catalysis ◽  
Mechanistic Studies ◽  
Alkyl Ethers ◽  
Nitrogen Substitution ◽  
Zinc Nickel

Mild methods to cleave the carbon-oxygen (C−O) bond in alkyl ethers could simplify chemical syntheses through the elaboration of these robust, readily available precursors. Here we report that dibromoboranes react with alkyl ethers in the presence of a nickel catalyst and zinc reductant to insert boron into the C−O bond. Subsequent reactivity can effect oxygen-to-nitrogen substitution or one-carbon homologation of cyclic ethers and more broadly streamline preparation of bioactive compounds. Mechanistic studies reveal a cleavage-then-rebound pathway via zinc/nickel tandem catalysis.

Deuterated Aryl Alkyl Ethers Synthesis via Nucleophilic Etherification of Aryl Alkyl Ethers and Thioethers with Deuterated Alcohols

Synlett ◽  
2019 ◽  
Vol 30 (15) ◽  
pp. 1805-1809
Author(s):  
Shuai Li ◽  
Xia Wang ◽  
Xin-Ge Yang ◽  
Gui-Quan Yu ◽  
Xue-Qiang Wang
Keyword(s):  
Transition Metal ◽  
Nucleophilic Aromatic Substitution ◽  
Aromatic Substitution ◽  
Mechanistic Studies ◽  
Reaction Conditions ◽  
Metal Free ◽  
Wide Range ◽  
Alkyl Ethers

A transition-metal-free etherification protocol that is capable of synthesizing deuterated ethers is described. A wide range of aryl alkyl ethers and thioethers were suitable for this transformation owing to the mild reaction conditions. Besides, a series of sterically bulky deuterated alcohols were successfully incorporated into cyano-substituted arenes. The results of mechanistic studies suggested this reaction might take place via nucleophilic aromatic substitution pathway.

Reactions of aryl diazonium salts and arylazo alkyl ethers. III. Substituent effects in the ionization of anti-arylazo ethyl ethers in ethanol

1978 ◽  
Vol 31 (7) ◽  
pp. 1519 ◽  
Author(s):  
TJ Broxton
Keyword(s):  
Substituent Effects ◽  
Parameter Analysis ◽  
Diazonium Salts ◽  
Resonance Effects ◽  
Inductive Effects ◽  
Alkyl Ethers

A dual substituent parameter analysis of substituent effects on the ionization of anti-arylazo ethyl ethers in ethanol shows that the reaction is affected primarily by inductive effects. The reaction is insensitive to resonance effects and an explanation for this behaviour is offered.

Reactions of Aryl Diazonium Salts and Arylazo Alkyl Ethers. IV. Substituent Effects on the Rates of Some Reactions of syn-Arylazo Ethyl Ethers in Ethanol

1979 ◽  
Vol 32 (5) ◽  
pp. 1031 ◽  
Author(s):  
TJ Broxton
Keyword(s):  
Substituent Effects ◽  
Diazonium Salts ◽  
Recombination Mechanism ◽  
Alkyl Ethers

Substituent effects on the rates of ionization (kIS), decomposition (kD) and syn-anti interconversion (kp) for a number of syn-arylazo ethyl ethers have been measured. The rates of ionization and syn-anti interconversion correlate well with sigma while the rates of decomposition correlate with σ+. Substituent effects on the ionization of the syn-ethers are compared to those for ionization of the anti-ethers. Substituent effects on the rate of syn-anti interconversion support the proposed ionization-recombination mechanism.

Reactions of aryl diazonium salts and arylazo alkyl ethers. VI. A comparison of the available methods for the measurement of the rate of ionization of (Z)-arylazo alkyl ethers in alcoholic solvents

1982 ◽  
Vol 35 (2) ◽  
pp. 319 ◽  
Author(s):  
TJ Broxton ◽  
MJ Mcleish
Keyword(s):  
Substituent Effects ◽  
Ionization Rate ◽  
New Method ◽  
Diazonium Salts ◽  
Advantages And Disadvantages ◽  
Diazonium Ions ◽  
Alkyl Ethers ◽  
Trapping Agent ◽  
Ionization Rates

Two previously reported methods for the determination of the ionization rate of (Z)-arylazo alkyl ethers by using x-naphtholate ions as a trapping agent are compared. A new method, which uses thiophenolate ions to trap the free diazonium ions formed in this ionization, is reported. This method is recommended in preference to the earlier methods because it includes a correction for the effect of the ionic strength of the solution on the rate of ionization. Rates measured by the thiophenolate method are consequently lower than those measured by either of the two previous methods. The advantages and disadvantages of the new method are discussed. The magnitude of salt effects and substituent effects on the ionization of (Z)- and (E)-arylazo alkyl ethers are compared.

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