On the diastereoselectivity of the aqueous-acid-catalyzed intramolecular aldol condensation of 3-oxocyclohexaneacetaldehydes

Authors
De Santis, B Iamiceli, AL Bettolo, RM Migneco, LM Scarpelli, R Cerichelli, G Fabrizi, G Lamba, D
Citation
B. De Santis et al., On the diastereoselectivity of the aqueous-acid-catalyzed intramolecular aldol condensation of 3-oxocyclohexaneacetaldehydes, HELV CHIM A, 81(12), 1998, pp. 2375-2387
Citations number
44
Categorie Soggetti
Chemistry & Analysis",Chemistry
Journal title
HELVETICA CHIMICA ACTA
ISSN journal
0018019X → ACNP
Volume
81
Issue
12
Year of publication
1998
Pages
2375 - 2387
Database
ISI
SICI code
0018-019X(1998)81:12<2375:OTDOTA>2.0.ZU;2-1
Abstract
The factors responsible for the diastereoselective formation of the 6-endo- hydroxybicyclo[2.2.2]octan-2-one by acid-catalyzed intramolecular aldol rea ction of 3-oxocyclohexaneacetaldehydes have been investigated. This study, carried out on (1SR,4RS,6RS)-6-hydroxybicyclo[2.2.2]oct la, (1SR,4RS,6SR)-6 -hydroxybicyclo[2.2.2]octan-2-one Ib, and 3,3-(ethylenedioxy)cyclohexaneace taldehyde 2a, allowed to demonstrate the absence of intramolecular I-I-bond ing in la as a stabilizing factor, and to ascertain the presence of unfavor able steric interactions in Ib.