73061-32-2Relevant academic research and scientific papers
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.
SYNTHESIS OF 1,2-GLYCOL MONOETHERS UTILIZING DECARBONYLATION OF α-ALKOXYACID CHLORIDES MEDIATED BY SAMARIUM DIIODIDE
Sasaki, Mitsuru,Collin, Jacqueline,Kagan, Henri B.
, p. 4847 - 4850 (2007/10/02)
A new synthesis of 1,2-glycol monoethers has been achived by utilizing decarbonylation of α-alkoxyacid chlorides mediated by samarium diiodide in the presence of ketones.This one-pot reaction works within a few minutes at room temperature.The structure of α-alkoxyacid chlorides (R2,R3)C(OR1)COCl2 tolerates various substitution patterns (R2=R3=H; R2=H; R3=Me or R2=R3=Me).
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.
Alcoxymethyltributyletains precurseurs d'alcoxymethyllithiums: application a la synthese de monoethers d'α-glycols et a l'homologation de cetones en aldehydes
Duchene, Alain,Mouko-Mpegna, David,Quintard, Jean-Paul
, p. 787 - 793 (2007/10/02)
Ethoxymethyltributyltin (obtained from diethoxymethyltributyltin, acetyl chloride and tributyltin hydride) and methoxymethyltributyltin (obtained from chloromethyl-methyl ether and tributylstannylmagnesium chloride) have been transmetallated with butyllithium to give the corresponding alkoxymethyl lithium reagents.This reaction, although usually performed in ether, is possible in a variety of other solvents thus simplifying some of the problems encountered during isolation of the products.The alkoxymethyllithiums obtained react with aldehydes and ketones to give cleanly the corresponding monoprotected α-glycols.Stereochemical trends were observed for hydratropaldehyde and 4-tertiarybutylcyclohexanone, while regiochemical trends were evaluated in the case of cyclohexen-2-one.Syntheis of aldehydes has been achieved in good yields from tertiary monoprotected α-glycols using conventional methods.
