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1,2‐Shift of a Carboxyl Group in a Wagner ‐ Meerwein Rearrangement
Author(s) -
Berner Daniel,
Cox D. Philip,
Dahn Hans
Publication year - 1982
Publication title -
helvetica chimica acta
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.74
H-Index - 82
eISSN - 1522-2675
pISSN - 0018-019X
DOI - 10.1002/hlca.19820650713
Subject(s) - chemistry , intramolecular force , yield (engineering) , stereochemistry , group (periodic table) , medicinal chemistry , character (mathematics) , cope rearrangement , organic chemistry , materials science , metallurgy , geometry , mathematics
On treatment with HSO 3 F in SO 2 C1F at 0°, 3‐hydroxy‐2,2‐dimethyl‐3‐phenyl‐propionic acid ( 1a ) is transformed into 2‐phenyl‐3‐methyl‐2‐butenoic acid ( 2a ) (isolated yield: 40–44%). Using monolabelled [3‐ 13 C]‐ 1a ( 1a *) and doubly labelled [1,3‐ 13 C 2 ]‐ 1a ( 1a **), the migration of HOOC (or a mechanistically equivalent group) was proved; a cross experiment established the intramolecular character of the rearrangement. By following the reaction at low temperature in an NMR. spectrometer, the formation of intermediates and side products was demonstrated.