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 gem-difluoroalkenes with alkenyl electrophiles.

Herein we develop a Ni-catalyzed defluorinative cross-electrophile coupling of gem-difluoroalkenes with alkenyl electrophiles that allowed the generation of C(sp2)-C(sp2) 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.