A nickel(0)/chiral N-heterocyclic carbene (NHC)-catalyzed fully intermolecular, enantioselective [2 + 2 + 2] cycloaddition of two enones and an alkyne has been developed to access enantioenriched cyclohexenes. A single diastereomer was obtained with a successive generation of four contiguous stereogenic centers. The absolute configuration of cyclohexene derivative 3aa was determined by X-ray diffraction and circular dichroism (CD) spectral studies.

An enantioselective hydrosilylation of prochiral ketones was achieved by using a catalytic amount of the readily accessible and air-and moisture-stable iridium complex [IrClA

Stereogenic Centers. -A diastereoselective access to cyclohexenes bearing four contiguous stereogenic centers through enantioselective [2 + 2 + 2] cycloaddition of two enones and one alkyne is developed. The process is also highly regioselective for unsymmetrical alkynes, but it is sensitive to both steric and electronic influences. -(KUMAR, R.; TOKURA, H.; NISHIMURA, A.; MORI, T.; HOSHIMOTO, Y.; OHASHI, M.; OGOSHI*, S.; Org. Lett. 17 (2015) 24, 6018-6021, http://dx.

The air‐ and moisture‐stable isoleucinol‐derived iridium carbene complex IRI in combination with AgBF4 efficiently catalyzes the stereoselective reduction of a variety of acetophenone derivatives and analogues at room temperature.