14869-39-7Relevant articles and documents
Lithiomethyl ethyl ether from chloromethyl ethyl ether via a DTBB-catalysed lithiation
Guijarro, Albert,Mancheno, Balbino,Ortiz, Javier,Yus, Miguel
, p. 1643 - 1650 (1996)
The reaction of equimolar amounts of chloromethyl ethyl ether (1) and a carbonyl compound [Bu(n)CHO, Bu(t)CHO, PhCHO, Pr(i)2CO, Bu(t)2CO, (CH2)4CO, 2-cyclohexenone, PhCOMe] with an excess of lithium powder (1:7 molar ratio) and a catalytic amount of DTBB (5 mol%) in THF at 0°C (Method A) leads, after hydrolysis, to the corresponding hydroxyethers 2. The reaction can be also carried out in a two-step process: tandem lithiation at -90°C and reaction with the electrophile [Bu(n)CHO,(CH2)4CO, PhCOMe, PhMe2SiCl, CO2, PhCN, PhCONMe2, CyNCO, PhN=CHPh] at -90 to -60°C (Method B).
Regioselective Vinylation of Remote Unactivated C(sp3)?H Bonds: Access to Complex Fluoroalkylated Alkenes
Wu, Shuo,Wu, Xinxin,Wang, Dongping,Zhu, Chen
, p. 1499 - 1503 (2019/01/04)
Regioselective incorporation of a particular functional group into aliphatic sites by direct activation of unreactive C?H bonds is of great synthetic value. Despite advances in radical-mediated functionalization of C(sp3)?H bonds by a hydrogen-atom transfer process, the site-selective vinylation of remote C(sp3)?H bonds still remains underexplored. Reported herein is a new protocol for the regioselective vinylation of unactivated C(sp3)?H bonds. The remote C(sp3)?H activation is promoted by a C-centered radical instead of the commonly used N and O radicals. The reaction possesses high product diversity and synthetic efficiency, furnishing a plethora of synthetically valuable E alkenes bearing tri-/di-/mono-fluoromethyl and perfluoroalkyl groups.
Direct Synthesis of α-Alkoxy Ketones by Oxidative C–O Bond Formation
Yu, Hui,Xu, Yilan,Fang, Yan,Dong, Rui
, p. 5257 - 5262 (2016/11/13)
A convenient method to prepare α-alkoxy ketones has been developed by oxidative coupling of aryl methyl ketones and alcohols. With aqueous tert-butyl hydroperoxide (6.0 equiv.) as the oxidant, tetrabutylammonium iodide (20 mol-%) as the catalyst, and TsNHNH2(1.0 equiv.) as the additive, ketones underwent direct alkoxylation to give α-methoxy or α-ethoxy ketones in moderate to good yields.