112944-92-0Relevant academic research and scientific papers
Efficient methods for the preparation of alkyl-aryl and symmetrical or unsymmetrical dialkyl ethers between alcohols and phenols or two alcohols by oxidation-reduction condensation
Shintou, Taichi,Mukaiyama, Teruaki
, p. 7359 - 7367 (2007/10/03)
Oxidation-reduction condensation via alkoxydiphenylphosphines (diphenylphosphinite esters) (1), generated in situ from chlorodiphenylphosphine (2) and alcohols, 2,6-dimethyl-1,4-benzoquinone (3), and phenols proceeds smoothly to afford alkyl-aryl ethers in good to high yields under neutral conditions. In a similar fashion, a new and efficient method for the preparation of symmetrical or unsymmetrical dialkyl ethers in good to high yields is established via tetrafluoro-1,4-benzoquinone (fluoranil) (4), alcohols, and 1 formed in situ from nBuLi-treated alcohols and 2. This method is applicable also to the etherification of chiral secondary or tertiary alcohols with retention or inversion of configurations. The inverted ethers are afforded by treating chiral alkoxydiphenylphosphines and achiral alcohols, while the reaction of achiral alkoxydiphenylphosphines and chiral alcohols forms retained ethers.
The α-Effect in Benzyl Transfers from Benzylphenylmethyl Sulfonium Salts to N-Methylbenzohydroxamate Anions
Fountain,Tad-y, Darlene B.,Paul, Timothy W.,Golynskiy, Mikhail V.
, p. 6547 - 6553 (2007/10/03)
The investigation of the occurrence of the α-effect in group transfers from phenyldialkyl sulfonium ions where one alkyl group is benzyl allows an assay of the effect of changing the nature of the C atom being transferred. The size of the α-effect responds to increasing electron demand, as methyl transfers do. Quantitative relationships between the size of the α-effect are established from both the nucleophilic side and the leaving group side of the SN2 transition state.
