- 作者: 何束英;周原朗;李慧莊
- 作者服務機構: 國立臺灣大學化學系
- 中文摘要: 研究非對稱第三胺與2-環已烯酮之光加成反應。電子從第三胺轉移至2-環已烯酮之激發態而產生胺陽離子自由基及環已烯酮陰離子自由基對。質子有選擇性的從胺陽離子自由基而轉移至環已烯酮陰離子自由基上而產生自由基對。加成產物由此自由基對結合而成。
- 英文摘要: Photochemical addition of nonsymmetrical tertiary amines to 2-cyclohexenone was investigated. Anelectron is transferred from tertiary amines to 2-cyclohexenone excited states to generate an aminium radi-cal and 2-cyclohexenone anion radical pair. Selective proton transfer from the aminium radical to 2-cyclo-hexenone radical anion generates an α-amino alkyl radical and 2-cyclohexenol allyl radical pair. The com-bination of the radical pair at the 3-position of the allyl radical gives the enol form of the amine-cyclo-hexenone adduct. Keto-enol tautomerism affords the final product.
- 中文關鍵字: photoinitiated electron transfer; aminium radical; stereoelectronic effect
- 英文關鍵字: --