Functional Group Transformations in Derivatives of 6-Oxoverdazyl

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• 作者：Marcin Jasi艅ski ; Jason S. Gerding ; Aleksandra Jankowiak ; Krzysztof G臋bicki ; Jaros艂aw Roma艅ski ; Katarzyna Jastrz臋bska ; Ajan Sivaramamoorthy ; Kristein Mason ; Donavan H. Evans ; Ma艂gorzata Celeda ; Piotr Kaszy艅ski
• 刊名：The Journal of Organic Chemistry
• 出版年：2013
• 出版时间：August 2, 2013
• 年：2013
• 卷：78
• 期：15
• 页码：7445-7454
• 全文大小：463K
• 年卷期：v.78,no.15(August 2, 2013)
• ISSN：1520-6904

文摘

Transformations of functional groups, such as OCH₂Ph, OCOPh, NO₂ and I, in 1,3,5-triphenyl-6-oxoverdazyls 1a鈥?b>1e were investigated in order to expand the range of synthetic tools for incorporation of the verdazyl system into more complex molecular architectures and to increase spin delocalization. Thus, Pd-catalyzed debenzylation of the OCH₂Ph group or basic hydrolysis of the OCOPh group gave the phenol functionality, which was acylated, but could not be alkylated. Orthogonal deprotection of diphenol functionality was also demonstrated in radical 1c. Pt-catalyzed reduction of the NO₂ group led to the aniline derivative, which was acylated. Attempted C鈥揅 coupling reactions to iodophenyl derivatives 1e and 5e were unsuccessful. Selected verdazyl radicals were characterized by EPR and electronic absorption spectroscopy, and results were analyzed with the aid of DFT computational methods.