Applications of phthalimide photochemistry to macrocyclic polyether, polythioether, and polyamide synthesis. |
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| Authors: | U C Yoon S W Oh J H Lee J H Park K T Kang P S Mariano |
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| Institution: | Department of Chemistry and Chemistry Institute for Functional Materials, Pusan National University, Pusan 609-735, Korea. ucyoon@hyowon.pusan.ac.kr |
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| Abstract: | Irradiation of phthalimides which contain N-linked omega-trimethylsilylmethyl-substituted polyether, polythioether, and polysulfonamide chains results in efficient production of the corresponding macrocyclic polyether, polythioether, and polysulfonamide products. These photocyclization reactions follow sequential single electron transfer (SET)-desilylation pathways. Only in the cases of phthalimides, bearing mixed ether-thioether N-substituents, do these excited-state cyclization reactions proceed with lower degrees of regioselectivity. This is a result of competitive desilylation and alpha-to-sulfur deprotonation reactions of the zwitterionic diradical intermediates formed by initial SET. |
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