Functional Group Transformations in Derivatives of 1,4-Dihydrobenzo[1,2,4]triazinyl Radical

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• 作者：Agnieszka Bodzioch ; Minyan Zheng ; Piotr Kaszy艅ski ; Greta Utecht
• 刊名：Journal of Organic Chemistry
• 出版年：2014
• 出版时间：August 15, 2014
• 年：2014
• 卷：79
• 期：16
• 页码：7294-7310
• 全文大小：694K
• ISSN：1520-6904

文摘

Transformations of functional groups OCOPh, OCH₂Ph, I, NO₂, and CO₂Me in Blatter鈥檚 radical derivatives 1鈥?b>5 were investigated in order to develop synthetic tools for incorporation of the benzo[1,2,4]triazinyl system into complex molecular architectures. Thus, basic hydrolysis of OCOPh or Pd-catalyzed debenzylation of OCH₂Ph gave phenol functionality, which was acylated and alkylated. Pd-catalyzed Suzuki, Negishi, Sonogashira, and Heck C鈥揅 cross-coupling reactions of iodo derivatives 1c, 1d, and 2d were also successful and efficient. Reduction of NO₂ in 1e led to aniline derivative 1t, which was reductively alkylated with hexanal and coupled to l-proline. Selected benzo[1,2,4]triazinyl radicals were characterized by EPR and electronic absorption spectroscopy, and the results were analyzed in tandem with DFT computational methods. Lastly, the mechanism for formation of the 1,4-dihydrobenzo[1,2,4]triazine ring was investigated using the B3LYP/6-31G(2d,p) method.