Photoinduced Bartoli Indole Synthesis by the Oxidative Cleavage of Alkenes with Nitro(hetero)arenes.

Given the unique charm of dipole chemistry, intercepting N-O=C dipoles precisely generated by designed processes to develop novel reactivity has become a seminal challenge. The polar fragmentation of 1,3,2-dioxazolidine species generated through the radical addition of excited nitro(hetero)arenes to alkenes represents a significantly underappreciated mechanism for generating N-O=C dipoles. Herein, we present a photoinduced Bartoli indole synthesis by the oxidative cleavage of alkenes with nitro(hetero)arenes.

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.

Nickel-catalyzed stereoselective reductive cross-coupling of -difluoroalkenes with alkenyl electrophiles.

Herein we develop a Ni-catalyzed defluorinative cross-electrophile coupling of -difluoroalkenes with alkenyl electrophiles that allowed the generation of C(sp)-C(sp) bonds. The reaction provided various monofluoro 1,3-dienes with broad functional group compatibility and excellent stereoselectivity. Synthetic transformations and applications to the modification of complex compounds were also demonstrated.