Synthesis Of Alkyl Aryl Ethers Research Articles

Synthesis of Alkyl Aryl Ethers by O-Arylation of Alcohols with Diaryliodonium Salts: Scope, Limitations, and Mechanism

AbstractWe describe the development of a C–O coupling reaction between aryl(2,4,6-trimethoxyphenyl)iodonium salts and aliphatic alcohols under weak base conditions. The scope of the reaction is presented, with 16 examples ranging in yield from moderate to high (54–96%). The limitations of the reaction are also presented. Mechanistic experiments reveal a complex network of reactions that include side reactions that generate arynes and oxidize the alcohol nucleophile.

Cross‐Coupling Reactions of Aryl Halides with Primary and Secondary Aliphatic Alcohols Catalyzed by an O,N,N‐Coordinated Nickel Complex

AbstractA synthesis of alkyl aryl ethers was achieved via the cross‐coupling of aryl halides with primary and secondary aliphatic alcohols catalyzed by a bench‐stable nickel complex supported by a monoanionic O,N,N‐tridentate ligand. This nickel‐catalyzed reaction proceeds smoothly in the absence of a phosphine ligand, affording alkyl aryl ethers in moderate to good yields.magnified image

Etherification of phenols by amines via transient diazonium intermediates

In this paper, the synthesis of alkyl aryl ethers from electron poor phenols and amines, using 1,3-propanedinitrite, is described. Due to the mild conditions, functionalized primary, secondary, and tertiary alkyl groups were successfully introduced, denoting a highly tolerant process that allows for unprotected alcohols and acetals. The reaction is thought to proceed through the formation of a diazonium intermediate that undergoes subsequent SN2 or SN1 reactions.

Decarboxylative C(sp3)−O Cross‐Coupling

AbstractAlkyl aryl ethers are an important class of compounds in medicinal and agricultural chemistry. Catalytic C(sp3)−O cross‐coupling of alkyl electrophiles with phenols is an unexplored disconnection strategy to the synthesis of alkyl aryl ethers, with the potential to overcome some of the major limitations of existing methods such as C(sp2)−O cross‐coupling and SN2 reactions. Reported here is a tandem photoredox and copper catalysis to achieve decarboxylative C(sp3)−O coupling of alkyl N‐hydroxyphthalimide (NHPI) esters with phenols under mild reaction conditions. This method was used to synthesize a diverse set of alkyl aryl ethers using readily available alkyl carboxylic acids, including many natural products and drug molecules. Complementarity in scope and functional‐group tolerance to existing methods was demonstrated.

Decarboxylative C(sp3 )-O Cross-Coupling.

Alkyl aryl ethers are an important class of compounds in medicinal and agricultural chemistry. Catalytic C(sp3 )-O cross-coupling of alkyl electrophiles with phenols is an unexplored disconnection strategy to the synthesis of alkyl aryl ethers, with the potential to overcome some of the major limitations of existing methods such as C(sp2 )-O cross-coupling and SN 2 reactions. Reported here is a tandem photoredox and copper catalysis to achieve decarboxylative C(sp3 )-O coupling of alkyl N-hydroxyphthalimide (NHPI) esters with phenols under mild reaction conditions. This method was used to synthesize a diverse set of alkyl aryl ethers using readily available alkyl carboxylic acids, including many natural products and drug molecules. Complementarity in scope and functional-group tolerance to existing methods was demonstrated.

Intermolecular C–O Coupling Using Hemicucurbituril Supported Ionic Liquid Phase Catalyst

Hemicucurbituril supported ionic liquid phase catalyst (HmCucSILP) has been synthesized by anchoring multilayer of ionic liquid ([Bmim]Cl) containing Pd(OAc)2 and X-phos on the surface of hemicucurbit[6]uril. The HmCucSILP was effectively employed in intermolecular C–O coupling of aryl halides with sodium alkoxides for the synthesis of alkyl aryl ethers.

Synthesis of Alkyl Aryl Ethers by Catalytic Williamson Ether Synthesis with Weak Alkylation Agents

For almost 70 years, there have been attempts to advance the Williamson ether synthesis process to allow the use of low-cost, noncarcinogenic, weak alkylating agents and avoid salt production. These attempts to produce a “green” version of Williamson ether synthesis have been based on the use of weak alkylating agents such as carboxylic acid esters at relatively high temperatures (approximately 200 °C) and pressures. However, none of the processes considered was suitable for industrial application because of the high concentration of the alkali metal carboxylates required. By increasing the temperature to above 300 °C, it has now proved possible to carry out Williamson ether synthesis as a homogeneous catalytic process. The large temperature increase significantly boosts the alkylating power of weak alkylating agents such as alcohols, carboxylic acid esters, and ethers derived from weak Bronsted acids, which are only weak alkylating agents at room temperature. At such temperatures, carboxylic acid esters ...

Solid-phase synthesis of alkyl aryl ethers via the Ullmann condensation.

Alkyl aryl ether formation is a frequently employed reaction in organic synthesis. Ullmann condensation is an alternative method to the widely used Mitsunobu reaction and is very useful in situations where application of the Mitsunobu reaction is limited. By application of this reaction to solid-phase synthesis of a series of alkyl aryl ethers, reaction conditions (catalyst, solvent, temperature, time, etc.) for a sterically hindered class of alcohols were investigated and optimized. A range of aryl halides was used to explore the scope of the reaction in solid phase.

Steroids. Part X. A convenient synthesis of alkyl aryl ethers

A simple synthesis of alkyl aryl ethers has been developed involving reaction between an alcohol, a phenol (or an enol), triphenylphosphine, and diethyl azodicarboxylate. By using this procedure several steroid, sugar, pyrimidine, and quinazoline ethers have been prepared.