Chakraborti, Asit K. ; Sharma, Lalima ; Nayak, Mrinal K. (2002) Influence of hydrogen bonding in the activation of nucleophiles: PhSH-(catalytic) KF in N-methyl-2-pyrrolidone as an efficient protocol for selective cleavage of alkyl/aryl esters and aryl alkyl ethers under nonhydrolytic and neutral conditions Journal of Organic Chemistry, 67 (8). pp. 2541-2547. ISSN 0022-3263
Full text not available from this repository.
Official URL: http://pubs.acs.org/doi/abs/10.1021/jo0163039
Related URL: http://dx.doi.org/10.1021/jo0163039
Abstract
The nucleophilicity of arenethiols can be augmented via hydrogen bonding with 'naked' halide anion. The activity of the halide anions follow the order F- >> Cl-∼Br-∼I- and is dependent on the countercation (Bu4N∼Cs∼K > Na >> Li). The solvent plays an important role in nucleophilic activation as well as regeneration of the effective nucleophile (e.g. ArS-) and those with high dielectric constant, high molecular polarizability, high donor number (DN), and low acceptor number (AN) are the most effective. Selective deprotection of alkyl/aryl esters and aryl alkyl ethers can be achieved under nonhydrolytic and neutral conditions by the treatment with thiophenol in 1-methyl-2-pyrrolidone (NMP) in the presence of a catalytic amount of KF. Aryl esters are selectively deprotected in the presence of alkyl esters and alkyl methyl ethers during intramolecular competitions.
Item Type: | Article |
---|---|
Source: | Copyright of this article belongs to American Chemical Society. |
ID Code: | 101049 |
Deposited On: | 19 Jan 2017 08:56 |
Last Modified: | 19 Jan 2017 08:56 |
Repository Staff Only: item control page