Demand-based thiolate anion generation under virtually neutral conditions: influence of steric and electronic factors on chemo- and regioselective cleavage of aryl alkyl ethers

Chakraborti, Asit K. ; Sharma, Lalima ; Nayak, Mrinal K. (2002) Demand-based thiolate anion generation under virtually neutral conditions: influence of steric and electronic factors on chemo- and regioselective cleavage of aryl alkyl ethers Journal of Organic Chemistry, 67 (18). pp. 6406-6414. ISSN 0022-3263

Full text not available from this repository.

Official URL: http://pubs.acs.org/doi/abs/10.1021/jo0256540

Related URL: http://dx.doi.org/10.1021/jo0256540

Abstract

Thiolate anions have been generated in a "demand-based" fashion under virtually neutral conditions for chemoselective deprotection of aryl alkyl ethers. Solvents play the critical role in making the reaction effective and should have high values of ε(>30), molecular polarizabilities (>10), and DN (>27) and low values of AN (<14). However, it is the combined effect of all of these physical properties that make a particular solvent effective. The reaction rates of cleavage of various aryl alkyl ethers are dependent on the steric crowding around the O-alkyl carbon and follow the order propargyl ≈ allyl ≈ benzyl > methyl > ethyl. Electron-withdrawing substituents increase the rate of ether cleavage reaction. The influence of the steric and electronic factors have been successfully exploited for selective deprotection of aryl alkyl ethers during inter- and intramolecular competitions.

Item Type:Article
Source:Copyright of this article belongs to American Chemical Society.
ID Code:101047
Deposited On:19 Jan 2017 09:06
Last Modified:19 Jan 2017 09:06

Repository Staff Only: item control page