單電子氧化誘導的化學轉換：碳-碳鍵的形成和選擇性噁唑烷重排

單電子氧化誘導的化學轉換：碳-碳鍵的形成和選擇性噁唑烷重排

Shafrizal Rasyid Atriardi, and Sang Kook Woo*

Department of Chemistry University of Ulsan, 93 Daehak-Ro Nam-gu, Ulsan 44610, Republic of Korea

[email protected]

摘要

可見光光氧催化是綠色可持續有機合成領域中一個重要且不斷成長的研究領域。單電子轉移 (Single-electron Transfer, SET) 是光過氧化催化的主要機理之一，我們的研究小組已對其進行了廣泛的研究，以開發更綠色的碳-碳鍵形成反應和噁唑烷重排反應。在這篇回顧中，我們將重點介紹我們在開發和應用中性矽自由基前體以生成烷基自由基，以及選擇性地將噁齊啶重組成硝基或酰胺方面的成果。

引言

近十年來，可見光光氧催化因其廉價、豐富、清潔的光源和溫和的反應條件，在可持續有機合成領域受到了廣泛的關注，並開發出了許多由可見光光氧催化促進的有機反應。¹單電子轉移 (SET) 會產生自由基物質，是光氧化催化反應的主要機制之一。根據催化循環中催化劑的氧化還原狀態，SET 機制可分為氧化淬火循環和還原淬火循環 (圖 1，(a)部分)。^1b,f,2 SET 機制的自發性很容易從光誘導電子轉移的吉布斯能量 (Δ)預測出來。G_PET = -F[E_red(A/A^--)) - E_ox(D^-+/D)] - w - ΔE_0,0），其中催化劑和底物的氧化還原電位可從文獻中獲得，或通過週期伏安法測定。我們的研究重點是 SET 在光氧化催化中的應用，利用過渡金屬基和有機光催化劑如 Ru(bpz)₃(PF₆)₂、Ir(dF(CF₃)ppy)₂(dtbpy)PF₆、Fukuzumi 的吖啶鎓鹽 (Acr⁺-Mes)、2,4,5,6-四(9H)-咔唑-9-基）-異酞腈 (4CzIPN) 和 2,4,5,6-四(3,6-二氯-9H-咔唑-9-基)異酞腈 (Cl-4CzIPN)，它們都是良好的氧化劑（圖 1，(b)部分）。由於有機光催化劑成本低且容易製備，因此我們特別青睞有機光催化劑。在這篇評論中，我們將介紹我們對中性硅基自由基前體的研究結果，這些前體可通過 SET 生成烷基自由基，並選擇性地將噁唑烷重排為硝基或酰胺。

圖 1. (a) 單電子轉移 (SET) 機理。(b) 流行的氧化劑光觸媒。(Ref. 1)

Conclusion

在這篇回顧中，我們總結了我們對於開發更環保、更永續的反應所做的貢獻，這些反應是透過光氧化催化中的 SET 機制來形成碳-碳鍵和重排噁唑烷。我們開發了烷氧基甲基、羥甲基和烯丙基的中性硅基前體，並將它們用於 Giese 反應、RPC 反應和亞胺加成反應中，以形成新的碳-碳鍵。這些反應提供了獲得廣泛有價值支架的途徑，例如醚、醇、2,3-二氫呋喃、α-氰基-γ-丁內酯、γ-丁內酯、烯丙基化合物、gem-二氟烯丙基、β-氨基醚和β-氨基醇。我們也證實了在光催化條件下，噁唑烷可選擇性地重排為硝基和酰胺。在乙腈、乙酸乙酯和丙酮等溶劑中，可選擇性地觀察到噁嗪基化合物重排為亞硝基化合物，而酰胺則通過弱基(如 CF₃CO₂^- 和 DMF) 促進的重排形成。我們正在進行的研究工作旨在進一步改良矽基烷基自由基前體，以生產和利用各種烷基自由基，並進一步探索噁唑烷的化學轉換。我們衷心希望我們的研究能為擴展生態友好的有機合成做出貢獻。

鳴謝

本研究獲得韓國政府（MSIT）資助的韓國國家研究基金會（NRF）的資助（NRF-2022R1A2C1005108 和 2021R1A4A1027480）。

商標。Amberlite^® (TDDP Specialty Electronic Materials US 8, LLC).

商標。

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