Transition-Metal-Free O-Arylation of Alcohols and Phenols with S-Arylphenothiaziniums

Abstract

Herein, we report the transition-metal-free O-arylation of alcohols and phenols with S-arylphenothiaziniums, which can be easily synthesized from boronic acids. Aryl substituents derived from arylboronic acids were selectively introduced into the hydroxy groups in alcohols and phenols, and a variety of aryl ethers were synthesized. This selectivity is supported by theoretical calculations.

Harnessing alcohols as sustainable reagents for late-stage functionalisation: synthesis of drugs and bio-inspired compounds

“…Various electronically decorated substituents were well tolerated including sugar 87e and steroid hormone estrone 87g (Scheme 40). 83 2.3.4 O-Phosphorylation of alcohol. Phosphorylation of alcohol is a fundamentally significant reaction in both chemical and biological science.…”

Recent Advances in Carbon‐Nitrogen/Carbon‐Oxygen Bond Formation Under Transition‐Metal‐Free Conditions

“…Apart from KOtBu, other alkoxides (including ethoxide, adamantanyl alkoxide, and fenchyl alkoxide) were also suitable coupling partners. Soon after this, the reactivity of KOtBu in other types of etherification reactions, including aryl alkyl ether formation via CÀ N bond cleavage of aryltrimethylammonium triflates (169, Scheme 35b), [100] C(sp 2 )-XMe (X=O and S) bonds cleavage (171, Scheme 35c), [26] alkoxylation of electro-deficient aromatic halides (173, Scheme 35d), [101] nucleophilic CÀ H bond etherification using halogenated thiophen derivatives as halogen transfer reagents (175, Scheme 35e) [102] and O-arylation of alcohols/phenols with S-arylphenothiaziniums (177) [103] (which can be easily synthesized from boronic acids, Scheme 36f) [104] , was further explored by different research groups to deliver a wide variety of diphenyl ethers and aryl alkyl ethers.…”

Recent Progress in C(sp2)–C(sp2) Bond Formation Using Ligand Coupling on Sulfur(IV)

“…13b Moreover, 17 could be used for the O -arylation of alcohols and phenols without transition metals. 14…”

“…13a A more convenient method for synthesizing 17 from readily available boronic acids was also developed. 13b Moreover, 17 could be used for the O -arylation of alcohols and phenols without transition metals. 14…”