Two prominent trifluoromethylation reagent classes join forces in a bench stable hypervalent iodosulfoximine CF3 transfer agent. We report its synthesis, properties and reactivity, opening up new possibilities in trifluoromethylation chemistry.

The direct trifluoromethylation of a variety of aliphatic alcohols using a hypervalent iodosulfoximine reagent afforded the corresponding ethers in moderate to good yields (14–72 %). Primary, secondary, and even tertiary alcohols, including examples derived from natural products, underwent this transformation in the presence of catalytic amounts of zinc bis(triflimide). Typical reaction conditions involved a neat mixture of 6.0 equivalents of the alcohol with 1.0 equivalent of the reagent, with the majority of reactions complete within 2 h with 2.5 mol % of the Lewis acid catalyst. Furthermore, experimental evidence was provided that the C−O bond‐forming process occurred via the coordination of the alcohol to the iodine atom and subsequent reductive elimination.

The first light-driven method for the α-trifluoromethoxylation of ketones is reported. Enol carbonates react with N -trifluoromethoxy-4-cyano-pyridinium, using the photoredox catalyst 4-CzIPN under 456 nm irradiation, affording the α-trifluoromethoxy ketones in ≤50% isolated yield and complete chemoselectivity. As shown by 29 examples, the reaction is general and proceeds very rapidly under batch (1 h) and flow conditions (2 min). Diverse product manipulations demonstrate the synthetic potential of the disclosed method in accessing elusive trifluoromethoxylated bioactive ingredients.

Dedicated to Prof. Antonio Togni on the occasion of his retirement and as a tribute to his immense contribution to the chemistry of hypervalent iodine.

We report an unprecedented domino polycyclization from readily available 2,4‐dienals and cyclic α,β‐unsaturated imines that is initiated by an iso‐Nazarov reaction. This Brønsted acid promoted reaction enables the concomitant formation of four bonds, three cycles, and four contiguous stereogenic centers to yield elaborated structures in a single operation. A range of fused hexacyclic molecules is obtained in a highly diastereoselective manner.

A general, scalable and easy to implement protocol is described for the coupling of thiosugars and various ortho‐functionalized S‐aryl S‐perfluoroalkyl sulfoximines. This dual photocatalysis methodology was developed with a commercial hydrogen atom transfer reagent and produced key structures that were transformed into original cyclic skeletons bearing previously undescribed chemical functions.

We describe the preparation of S‐perfluoroalkyl benzodithiazole trioxides as radical perfluoroalkylating reagents. Their syntheses were performed on a multi‐gram scale by an oxidative cyclization connecting the nitrogen of a sulfoximine and a sulfur atom previously introduced in the ortho position of this group. The structures and properties of these new molecules were carefully examined by X‐Ray diffraction, DFT calculations and cyclic voltammetry. These data clearly highlight the enhanced reactivity of these cyclic sulfoximines compared to their open analogues. This was confirmed by photoredox catalysis experiments that revealed interesting reactivity, most especially for the introduction of di‐ and monofluoroalkyl chains.

We report an unprecedented domino polycyclization from readily available 2,4‐dienals and cyclic α,β‐unsaturated imines that is initiated by an iso‐Nazarov reaction. This Brønsted acid promoted reaction enables the concomitant formation of four bonds, three cycles, and four contiguous stereogenic centers to yield elaborated structures in a single operation. A range of fused hexacyclic molecules is obtained in a highly diastereoselective manner.