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The prevalence of stereogenic \u03b2\u2010methyl ketone structural motifs in bioactive compounds and natural products has long motivated the development of enantioselective strategies toward their synthesis. Herein, we have rationally designed a Rh\u2010catalyzed asymmetric monohydrogenation of readily\u2010available \u03b2\u2032\u2010methylene conjugated enones with high efficiency and remarkable site\u2010selectivity and enantioselectivity control for the practical construction of enantioenriched \u03b2\u2032\u2010methyl unsaturated enones that are difficult to access by other methods. Control experiments revealed that the conjugated C=C bond in \u03b2\u2032\u2010methylene conjugated enones plays a significant role in enhancing the reactivity of monohydrogenation. This methodology is applicable for the preparation of chiral \u03b2,\u03b2\u2032\u2010dimethyl ketones through consecutive double asymmetric hydrogenation of \u03b2,\u03b2\u2032\u2010dimethylene ketones. Detailed mechanistic investigation and DFT studies further provided strong support for a unique processive catalysis pathway for double asymmetric hydrogenation. The synthetic utilities have been demonstrated in the concise synthesis of several key intermediates for bioactive molecules, asymmetric total synthesis of natural products (<jats:italic>S<\/jats:italic>)\u2010(+)\u2010<jats:italic>ar<\/jats:italic>\u2010Turmerone and (<jats:italic>S<\/jats:italic>)\u2010(+)\u2010dihydro\u2010<jats:italic>ar<\/jats:italic>\u2010Turmerone, and two <jats:italic>C<\/jats:italic><jats:sub>2<\/jats:sub>\u2010symmetric chiral spirocyclic diol frameworks.<\/jats:p>","DOI":"10.1002\/anie.202414449","type":"journal-article","created":{"date-parts":[[2024,12,10]],"date-time":"2024-12-10T23:55:13Z","timestamp":1733874913000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":10,"title":["Catalytic Asymmetric Synthesis and Applications of Stereogenic \u03b2\u2032\u2010Methyl Enones and \u03b2,\u03b2\u2032\u2010Dimethyl 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