REGIOSELECTIVITY IN PHOTOCHEMICAL CHLOROCARBONYLATION OF CARBONYL-COMPOUNDS

Citation
A. Bashirhashemi et al., REGIOSELECTIVITY IN PHOTOCHEMICAL CHLOROCARBONYLATION OF CARBONYL-COMPOUNDS, Journal of organic chemistry, 59(8), 1994, pp. 2132-2134
Citations number
31
Categorie Soggetti
Chemistry Inorganic & Nuclear
ISSN journal
00223263
Volume
59
Issue
8
Year of publication
1994
Pages
2132 - 2134
Database
ISI
SICI code
0022-3263(1994)59:8<2132:RIPCOC>2.0.ZU;2-8
Abstract
Photochemical chlorocarbonylation of a series of cyclic and acyclic ca rbonyl compounds shows remarkable regioselectivity and gives beta- or gamma-substituted products in reasonable yields. Irradiation of cyclop entanone in oxalyl chloride followed by esterification with methanol g ave methyl 3-oxocyclopentanecarboxylate (4). Similarly, photochemical chlorocarbonylation of cyclobutanone yielded methyl 3-oxocyclobutaneca rboxylate (6). Application of the chlorocarbonylation reaction to 3-pe ntanone gave methyl 4-oxohexanoate (8) and dimethyl 4-oxopimelate (9). When a mixture of 3-methylbutanoic acid and oxalyl chloride was irrad iated, dimethyl 3-methylglutarate (11) was obtained after methanolysis . A kinetically-controlled mechanism for the photochemical process was deduced.