The development of straightforward synthesis of regio- and stereodefined alkenes with multiple aliphatic substituents under mild conditions is an unmet challenge owing to competitive β-hydride elimination and selectivity issues. Herein, we report the nickel-catalyzed intermolecular cross-dialkylation of alkynes devoid of directing or activating groups to afford multiple aliphatic substituted alkenes in a syn-selective fashion at room temperature. The combination of two-electron oxidative cyclometallation and single-electron cross-electrophile coupling of nickel enables the syn-cross-dialkylation of alkynes at room temperature. This reductive protocol enables the sequential installation of two different alkyl substituents onto alkynes in a regio- and stereo-selective manner, circumventing the tedious preformation of sensitive organometallic reagents. The synthetic utility of this protocol is demonstrated by efficient synthesis of multi-substituted unfunctionalized alkenes and diverse transformations of the product.

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Direct γ-C(sp3)-arylation of unactivated electron-rich enones is a long-standing challenge. Herein, we report a mild Pd-catalyzed method for direct γ-C(sp3)-arylation of various unactivated β-alkoxy cyclohexenones. The method is not only...

Access to 1,3-conjugated enynes with defined stereoselectivity is highly desirable and challenging. Herein, we report a facile synthesis of stereodefined 1,3-conjugated enynes via Nicatalyzed intermolecular cross-alkylalkynylation of alkynes with unsaturated carbonyl compounds and alkynes or alkynyl silicates. The operational simple protocol proceeds at room temperature and tolerates a wide range of functional groups, providing an attractive alternative to carbonyl-tethered trisubstituted conjugated 1,3enynes from easily accessible starting materials.

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