ISSN:
0018-019X
Keywords:
Chemistry
;
Organic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
1-(Alkoixycarbonyl)heptalene-2-carboxylic acids as well as 2-(alkoxycarbonyl)heptalene-1-carboxylic acids react with the iminium salt formed from N,N-dimethylformamide (DMF) and oxalyl chloride, in the presence of an alcohol, to yield the corresponding cyclic ‘ortho’ -anhydrides (ψ-esters; cf. Schemes 2,3,6, and 8). When the alkoxy moiety of the acids and the alcohols is different, then diastereoisomeric ‘ortho’ -anhydrides are formed due to the non-planarity of the heptalene skeleton. The approach of the alcohol from the β-side is strongly favored (cf. Scheme 5 and Table 1). This effect can be attributed to the bent topology of the heptalene skeleton which sterically hinders the approach of the nucleophile from the α-side of the postulated intermediates, i.e. the charged O-alkylated anhydrides of type 19 (cf. Scheme 6). Whereas the ‘ortho’-anhydrides with four substituents in the ‘peri’ -positions of the heptalene skeleton are configurationally stable up to 100°, the ‘ortho’ -anhydrides with only three ‘peri’ -substituents slowly epimerize at 100° (cf. Scheme 7) due to the thermally induced inversion of the configuration of the heptalene skeleton.
Additional Material:
2 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/hlca.19870700602
