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Title: | Photoredox Catalyzed Single C−F Bond Activation of Trifluoromethyl Ketones: A Solvent Controlled Divergent Access of gem-Difluoromethylene Containing Scaffolds |
Authors: | Ghosh, S. Qu, Z-W. Roy, S. Grimme, S. Chatterjee, I. |
Keywords: | cyclic ketals C−F bond activation density functional calculations fluorinated solvent gem-difluoromethylene unit photoredox catalysis |
Issue Date: | 23-Oct-2024 |
Abstract: | Selective defluorinative functionalization of trifluoromethyl ketones is a long-standing challenge owing to the exhaustive mode of the process. To meet the demands for the installation of the gem-difluoromethylene unit for the construction of the molecular architectures of well-known pharmaceuticals and agrochemicals, a distinct pathway is thereby highly desirable. Here, a protocol is introduced that allows the divergent synthesis of gem-difluoromethylene group containing tetrahydrofuran derivatives and linear ketones via single C−F bond activation of trifluoromethyl ketones using visible-light photoredox catalysis in the presence of suitable olefins as trapping partner. The choice of appropriate solvent and catalyst plays a significant role in controlling the divergent behavior of this protocol. Highly reducing photo-excited catalysts are found to be responsible for the generation of α,α-difluoromethyl ketone (DFMK) radicals as the key intermediate via a SET process. This protocol also results in a high diastereoselectivity towards the formation of partially fluorinated cyclic ketal derivatives with simultaneous construction of one C−C and two C−O bonds. State-of-the-art DFT calculations are performed to address the origin of diastereoselectivity as well as the divergence of this protocol. |
URI: | http://dspace.iitrpr.ac.in:8080/xmlui/handle/123456789/4754 |
Appears in Collections: | Year-2023 |
Files in This Item:
File | Description | Size | Format | |
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Photoredox Catalyzed full text.pdf | 11.42 MB | Adobe PDF | View/Open Request a copy |
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