Premium
Nucleophilic 1,2‐Shifts of Alkoxycarbonyl and Carboxylate Groups in the Benzilic‐Acid Type Rearrangement of α,β‐Dioxobutyric Esters
Author(s) -
Gowal Heike,
Dao Lê H.,
Dahn Hans
Publication year - 1985
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.19850680121
Subject(s) - chemistry , isopropyl , steric effects , hydrate , nucleophile , medicinal chemistry , carboxylate , hydrolysis , alkyl , stereochemistry , organic chemistry , catalysis
tert ‐Butyl α,β‐dioxobutyrate (hydrate; 1d ) undergoes, at medium or high pH, the benzilic‐acid rearrangement with exclusive 1,2‐shift of the COO( t ‐Bu) group; the same is true for the corresponding isopropyl ester 1c and ethyl ester 1b at high pH, whereas at lower pH, the overall picture of these reactions is complicated by concurrent hydrolysis of the ester, followed by a 1,2‐shift of the COO − group. Consequently, the shift of these electron‐attracting groups cannot be considered to be systematically disfavoured (compared, e.g. , with alkyl‐group shifts). Kinetic measurements of the rearrangement show for both esters (as well as for the analogous ethyl ester 1b , and also for ethyl 3‐cyclopropyl‐α,β‐dioxopropionate ( 4 )) a characteristic rate profile: at relatively low pH, k is proportional to [HO − ], approaching saturation with increasing [HO − ] (interpreted as complete transformation of the substrate into the hydrate monoanion), which is followed at higher pH by another rate increase with k proportional to [HO − ] (probably due to the reaction of the hydrate dianion). The similarity of k values for 1b‐d shows that in the shift of COOR steric hindrance caused by R is negligible.