ISSN:
0009-2940
Keywords:
Cadmium sulfide
;
Paired photoelectrolysis
;
γ,δ-Unsaturated amines
;
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
Irradiation of methanolic cadmium sulfide suspensions in the presence of Schiff bases and cyclopentene opens an easy access to new γ,δ-unsaturated amines. Their formation can be described as a kind of paired photoelectrolysis induced by the photogenerated electron-hole pair trapped at reactive surface sites of CdS. At the reductive site the imine is converted to an α-aminobenzyl radical by a proton-coupled electron transfer, while at the oxidative site cyclopentene is transformed to the cyclopentenyl radical through deprotonation of the intermediate radical cation. C-C coupling of these radicals affords the addition products. Competitive dimerisation of the radicals produces hydrodimers of the imines and dehydrodimers of the olefin, as demonstrated in the case of 1-phenylcyclohexene. Using optical active imines, we found no significant diastereoselectivity. In the absence of an olefin the alcoholic solvent was added to the imine. The molecular structure of one hydrodimer was resolved by X-ray analysis. When CdS/Pt was used as photocatalyst, hydrolysis products of the imine were formed, suggesting involvement of an intermediate OH radical.
Additional Material:
2 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/cber.19961290808
