Enantio‐ and diastereoselective synthesis of trans‐2,3‐disubstituted indanones is achieved by intramolecular hydroacylation of 2‐alkenylbenzaldehydes bearing trisubstituted alkenyl groups under cobalt‐chiral diphosphine catalysis. Notably, a high level of enantioselectivity is induced regardless of the stereochemistry (E/Z ratio) of the alkenyl group of the starting material. Deuterium‐labeling experiments shed light on the productive reaction pathways of the E‐ and Z‐isomers.

Cobalt catalysts promote ring-opening coupling between cyclopropanols and unactivated alkynes to give β-alkenyl ketones or cyclopentenols with exquisite chemoselectivity control.

Enantio-and diastereoselective synthesis of trans-2,3-disubstituted indanones is achieved by intramolecular hydroacylation of 2-alkenylbenzaldehydes bearing trisubstituted alkenyl groups under cobalt-chiral diphosphine catalysis. Notably,ahigh level of enantioselectivity is induced regardless of the stereochemistry (E/Z ratio) of the alkenyl group of the starting material. Deuterium-labeling experiments shed light on the productive reaction pathways of the E-and Z-isomers. Scheme 3. Proposed catalytic cycle and rationale for the E/Z-insensitive enantioselectivity. Scheme 4. Selected product transformations. mCPBA = m-chloroperbenzoic acid, Tf = trifluoromethanesulfonyl.