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Tandem Acid/Pd‐Catalyzed Reductive Rearrangement of Glycol Derivatives
Author(s) -
Schmidt Tanno A.,
Ciszek Benjamin,
Kathe Prasad,
Fleischer Ivana
Publication year - 2020
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.202000251
Subject(s) - formic acid , aldehyde , chemistry , catalysis , formate , substrate (aquarium) , ligand (biochemistry) , organic chemistry , tandem , sulfonic acid , combinatorial chemistry , medicinal chemistry , biochemistry , oceanography , receptor , geology , materials science , composite material
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 Pd II or Pd 0 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.