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Quantitative hydrogenation was observed when 1.0\u2005mol\u2009% of a methyl\u2010substituted phosphetane oxide was employed as the catalyst. The procedure is highly selective towards activated double bonds, tolerating a variety of functional groups that are usually prone to reduction. In total, 25 alkenes and two alkynes were hydrogenated to the corresponding alkanes in excellent yields of up to 99\u2009%. Notably, less active poly(methylhydrosiloxane) could also be utilized as the terminal reductant. 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