Premium
Effect of Supramolecular Inclusion on the 1,2‐Rearrangement of Free Radicals
Author(s) -
Chen Ying,
Kervio Eric,
Rétey János
Publication year - 2002
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 - 10.1002/1522-2675(200202)85:2<552::aid-hlca552>3.0.co;2-1
Subject(s) - chemistry , radical , photodissociation , photochemistry , free radical addition , supramolecular chemistry , cyclodextrin , alkoxy group , free radical reaction , stereochemistry , medicinal chemistry , organic chemistry , molecule , alkyl
The free radicals 3‐ethoxy‐2‐(ethoxycarbonyl)‐3‐oxopropyl ( 1 . ) and 3‐ethoxy‐2‐(ethoxycarbonyl)‐2‐methyl‐3‐oxopropyl ( 2 . ) were generated by photolysis of perester precursors in i ) hexane solution, ii ) in the presence of β ‐cyclodextrin, and iii ) in NaY zeolite. While free radicals in solution are reluctant to rearrange, they do so when encapsulated in β ‐cyclodextrin or NaY zeolite. The coenzyme‐B 12 ‐dependent enzymic rearrangement of methylmalonyl‐CoA to succinyl‐CoA could be mimicked by photochemical generation of an analogue of the putative intermediate radical in a molecular container.