Anaerobic 1,2-/1,3-Hydroxytrifluoromethylation of Unactivated Alkenes Enabled by Photoexcited Nitroarenes.

An anaerobic 1,2-/1,3-hydroxytrifluoromethylation of unactivated alkenes is described. This reaction proceeds in mild and environmentally friendly conditions without photocatalyst and metal catalyst, allowing access to a wide range of β- and γ-trifluoromethyl alcohols. Preliminary mechanistic investigations indicate that the accomplishment of this protocol relies on the dual functionality of the photoexcited triplet nitroarenes, which serve as the oxygen atom source and enable the single-electron transfer (SET) process with CFSONa.

Nickel-Catalyzed Stereoconvergent C(sp)-F Alkenylation of Monofluoroalkenes.

The stereoconvergent synthesis of a single stereoisomer from /-olefin mixtures remains one of the foremost challenges in organic synthesis. Herein, we describe a nickel-catalyzed stereoconvergent cross-coupling between - and -mixed monofluoroalkenes and alkenyl electrophiles, which allows the construction of C(sp)-C(sp) bonds. This defluorinative transformation offers facile access to various 1,3-dienes with -selectivity and good functional group tolerance.

Radical Addition-Enabled C-C σ-Bond Cleavage/Reconstruction to Access Functional Indanones: Total Synthesis of Carexane L.

C-C σ-bond cleavage and reconstruction is a significant tool for structural modification in synthetic chemistry but it remains a formidable challenge to perform on unstrained skeletons. Herein, we describe a radical addition-enabled C-C σ-bond cleavage/reconstruction reaction of unstrained allyl ketones to access various functional indanones bearing a benzylic quaternary center. The synthetic utility of this method has been showcased by the first total synthesis of carexane L, an indanone-based natural product.