Switchable In Situ SO₂ Capture and CF₃ Migration of Enol Triflates with Peroxyl Compounds under Iron Catalysis

Abstract

Switchable in situ SO2 capture and CF3 migration of enol triflates with peroxyl compounds under iron catalysis are presented. By regulating the structure of peroxides, a variety of keto-functionalized dialkyl sulfones and α-trifluoromethyl ketones were selectively synthesized in good yields under mild conditions.

Recent Advances in Non-Precious Metal Catalysis

“…Other notable advances in the field of iron catalysis during this period include: (1) Enzymatic Nitrogen Insertion into Unactivated C−H Bonds; 79 Iron Catalysis; 82 (5) Visible-Light-Promoted Fe(III)-Catalyzed N−H Alkylation of Amides and N-Heterocycles. 83 The field of nonprecious metal catalysis continues to garner attention from numerous research groups in both academia and industry.…”

Iron-Catalyzed Alkoxyl Radical-Induced C–C Bond Cleavage/gem-Difluoroalkylation Cascade

“…In particular, the ring expansion/functionalization is still challenging and rarely reported. In recent years, our group has been focused on developing concise and efficient radical-mediated C–C bond cleavage cascades, in which functionalized carbon-centered radical intermediates were first formed. Thus, we envision that difluoroenoxysilanes would be promising radical acceptors for capturing these intermediates and producing new types of fluorine-containing compounds (Scheme B).…”

“…In addition, using 1,1-diphenylethylene as the radical acceptor led to alkenyl ketone 11a in 52% yield, which also provides support for a radical pathway. On the basis of these primary results, the literature, and refs and , a radical pathway was proposed by using 5a and 2a as model substrates (Scheme b). First, single-electron reduction of hydroperoxide 5a with an Fe­(II) catalyst generates alkoxyl radical intermediate I and Fe­(III) species.…”

Oxidation of α-Trifluoromethyl and Nonfluorinated Secondary Alcohols to Ketones Using a Nitroxide Catalyst

“…Trifluoromethyl ketones (TFMKs) have proved to be useful starting materials for a number of synthetic transformations. 1,2 They can also be used as synthons for rapid 19 F-labelling of compounds. 3 TFMKs are also interesting in their own right.…”