119809-68-6Relevant academic research and scientific papers
Continuous Flow Acylation of (Hetero)aryllithiums with Polyfunctional N,N-Dimethylamides and Tetramethylurea in Toluene
Djukanovic, Dimitrije,Filipponi, Paolo,Heinz, Benjamin,Knochel, Paul,Mandrelli, Francesca,Martin, Benjamin,Mostarda, Serena
, p. 13977 - 13981 (2021)
The continuous flow reaction of various aryl or heteroaryl bromides in toluene in the presence of THF (1.0 equiv) with sec-BuLi (1.1 equiv) provided at 25 °C within 40 sec the corresponding aryllithiums which were acylated with various functionalized N,N-
Tandem Acid/Pd-Catalyzed Reductive Rearrangement of Glycol Derivatives
Ciszek, Benjamin,Fleischer, Ivana,Kathe, Prasad,Schmidt, Tanno A.
supporting information, p. 3641 - 3646 (2020/03/25)
Herein, we describe the acid/Pd-tandem-catalyzed transformation of glycol derivatives into terminal formic esters. Mechanistic investigations show that the substrate undergoes rearrangement to an aldehyde under [1,2] hydrogen migration and cleavage of an oxygen-based leaving group. The leaving group is trapped as its formic ester, and the aldehyde is reduced and subsequently esterified to a formate. Whereas the rearrangement to the aldehyde is catalyzed by sulfonic acids, the reduction step requires a unique catalyst system comprising a PdII or Pd0 precursor in loadings as low as 0.75 mol % and α,α′-bis(di-tert-butylphosphino)-o-xylene as ligand. The reduction step makes use of formic acid as an easy-to-handle transfer reductant. The substrate scope of the transformation encompasses both aromatic and aliphatic substrates and a variety of leaving groups.
