Nickel-Catalyzed Asymmetric Reductive [3 + 2] Annulation of <i>o</i>‑Haloaromatic β‑Alkenyl Ketones with Alkynes via Alkene Isomerization: Enantioselective Synthesis of 1‑Alkenyl 1<i>H</i>‑Inden-1-ols

A nickel-catalyzed asymmetric reductive [3 + 2] annulation of o-haloaromatic β-alkenyl ketones with alkynes through alkyne dicarbofunctionalization and alkene isomerization cascades is disclosed, enabling the formation of highly enantiomerically enriched 1-alkenyl 1H-inden-1-ols that possess an important stereogenic quaternary carbon and an active alkene unit. This reaction shows notable features of a broad substrate scope and excellent controlled stereo-, chemo-, and regio-selectivity and is useful for synthetic applications to the construction of diverse chiral tertiary alcohol system-containing sterically demanding structures and their derivatized chiral building blocks.