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  • 09월 05일 17시 이후 : 초록수정 불가능, 일정확인 및 검색만 가능

제120회 대한화학회 학술발표회, 총회 및 기기전시회 안내 Single electron transfer strategy for reductive cyclization and oxidative cycloaddition reactions using iron polypyridyl complexes

2017년 8월 24일 15시 24분 13초
ORGN.O-2 이곳을 클릭하시면 발표코드에 대한 설명을 보실 수 있습니다.
목 09시 : 15분
Organic Chemistry - Oral Presentations of Young Scholars in Organic Division
저자 및
Joon Young Hwang, Eun Joo Kang*
Department of Applied Chemistry, Kyung Hee University, Korea

Reductive radical cyclization using low-valent iron pentacarbonyl [Fe(CO)5] to generate radical species from alkyl iodides was achieved. A range of pyrrolidines, tetrahydrofurans, and carbocycles were synthesized via 5-exo cyclization reactions of alkyl radical intermediates generated by electron transfer from a system involving Fe(CO)5, 1,10-phenanthroline, and diisopropylamine. In addition, we have successfully applied to the tandem radical reactions with Michael acceptor. We have found the presence of Fe2+(phen)3 species during the reaction through UV-vis absorption spectroscopy and electrospray ionization mass spectrometry (ESI-MS), which are the distinct evidence that Fe and phenanthroline system acts as electron donor agents. Moreover, we have proved that radical pathway is main route by the radical clock reaction, TEMPO experiment, and electron paramagnetic resonance (EPR) studies to investigate iron(III) complex and phenanthroline radical anion species. Especially, iron(III) polypyridyl complexes can be used as single-electron oxidants with tertiary amines or anilines [Eox = 0.8-1.0 V] for formation amine radical cation as a hydrogen atom source. In this regard, we planned oxidative reaction of tertiary amines with iron polypyridyl complexes. After amine is oxidized by iron(III) complex, deprotonation of amine radical cation offers α-amino radical species, which is reactive to α,β-unsaturated carbonyl compounds as a radical acceptors. Herein, we present reductive radical cyclization of iodoalkene and oxidative cycloaddition of tertiary amines with maleimides under mild reaction condition.