Applications of phthalimide photochemistry to macrocyclic polyether, polythioether, and polyamide synthesis.
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.
Yoon
U C
UC
Department of Chemistry and Chemistry Institute for Functional Materials, Pusan National University, Pusan 609-735, Korea. ucyoon@hyowon.pusan.ac.kr
Oh
S W
SW
Lee
J H
JH
Park
J H
JH
Kang
K T
KT
Mariano
P S
PS
D004987:Ethers / Q000737:chemistry*; D009757:Nylons / Q000737:chemistry*; D010777:Photochemistry; D010797:Phthalimides / Q000737:chemistry*; D013057:Spectrum Analysis
D004987:Ethers; D009757:Nylons; D010797:Phthalimides; C037431:phthalimide