Wenshan Wang, Gonghong Qiu, Wenjing Ma, Guiyun Chen, Lingbo Qu, Tianyi Shang, Yan Liu and Bing Yu
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Photoinduced radical germyloximation of activated alkenes†
This study unveils a photoinduced radical germyloximation strategy for the bifunctionalization of activated alkenes under photocatalyst-, metal-, and additive-free conditions. This methodology leverages the homolytic cleavage of the O–NO bond in tert-butyl nitrite under light irradiation to generate a reactive tert-butoxyl radical and a persistent nitric oxide (NO) radical. The tert-butoxyl radical can act as a hydrogen atom transfer (HAT) reagent of a germane hydride to afford germyl radicals that subsequently undergo regioselective addition to activated alkenes, followed by cross-coupling with the NO radical to yield α-germyl oximes. Late-stage germyloximation of pharmaceutically relevant complex molecules underscores the synthetic applicability and downstream derivatization of α-germyl oxime derivatives highlights the practical versatility. Overall, this novel protocol substantially expands the repertoire of tools for constructing structurally distinct 3D aliphatic germanes and holds considerable promise for advancing germanium-based chemical research.
期刊介绍:
Green Chemistry is a journal that provides a unique forum for the publication of innovative research on the development of alternative green and sustainable technologies. The scope of Green Chemistry is based on the definition proposed by Anastas and Warner (Green Chemistry: Theory and Practice, P T Anastas and J C Warner, Oxford University Press, Oxford, 1998), which defines green chemistry as the utilisation of a set of principles that reduces or eliminates the use or generation of hazardous substances in the design, manufacture and application of chemical products. Green Chemistry aims to reduce the environmental impact of the chemical enterprise by developing a technology base that is inherently non-toxic to living things and the environment. The journal welcomes submissions on all aspects of research relating to this endeavor and publishes original and significant cutting-edge research that is likely to be of wide general appeal. For a work to be published, it must present a significant advance in green chemistry, including a comparison with existing methods and a demonstration of advantages over those methods.