Premium
Rearrangement of 2‐(4‐Hydroxyalkyl)‐1,3‐dioxolanes to 2‐Hydroxyethyl Alkanoic Esters by 1,5‐Hydride Shift – An Unprecedented Intramolecular Redox Reaction
Author(s) -
Krohn Karsten,
Flörke Ulrich,
Höfker Uwe,
Träubel Marion
Publication year - 1999
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/(sici)1099-0690(199912)1999:12<3495::aid-ejoc3495>3.0.co;2-0
Subject(s) - chemistry , intramolecular force , hydride , redox , deuterium , carbenium ion , medicinal chemistry , reaction mechanism , rearrangement reaction , ion , catalysis , stereochemistry , organic chemistry , hydrogen , physics , quantum mechanics
2‐(4‐Hydroxyalkyl)‐1,3‐dioxolanes ( 3a/3b , 5 – 7 ) undergo an acid‐catalyzed rearrangement to give 2‐hydroxyethyl alkanoic esters 8 – 11 . The postulated mechanism, proceeding via the benzylic carbenium ion B and the 1,3‐dioxolan‐2‐ylium cation C , is supported by the stereochemistry of the reaction and the results of deuterium labeling experiments.