73061-32-2Relevant articles and documents
Tandem Acid/Pd-Catalyzed Reductive Rearrangement of Glycol Derivatives
Ciszek, Benjamin,Fleischer, Ivana,Kathe, Prasad,Schmidt, Tanno A.
, 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.
ELECTRONIC STRUCTURE AND REACTIVITY OF 1-OXASPIROALKANES
Kas'yan, L.I.,Gorb, L.G.,Galafeeva, M.F.,Stepanova, N.V.,Minaev, E.N.,Dryuk, V.G.
, p. 320 - 326 (2007/10/02)
The behavior of the epoxides of methylenecycloalkanes (1-oxaspiroalkanes) in reaction with methanol was studied.It was shown that the direction of the reaction depends on the nature of the medium; in an alkaline medium opening of the epoxide ring takes place regiospecifically according to the Krasuskii rule, and in an acidic medium it takes place mainly in the reverse direction.The reactivity of the epoxides and its dependence on the nature of the acyclic fragment were studied by quantum-chemical calculation and kinetic investigations.
