Catalytic Asymmetric Hydrogenation of Pyrimidines

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<jats:title>Abstract</jats:title><jats:p>The asymmetric hydrogenation of pyrimidines proceeded with high enantioselectivity (up to 99 % <jats:italic>ee</jats:italic>) using an iridium catalyst composed of [IrCl(cod)]<jats:sub>2</jats:sub>, a ferrocene‐containing chiral diphosphine ligand (Josiphos), iodine, and Yb(OTf)<jats:sub>3</jats:sub> (cod=1,5‐cyclooctadiene). The chiral catalyst converted various 4‐substituted pyrimidines into chiral 1,4,5,6‐tetrahydropyrimidines in high yield. The lanthanide triflate is crucial for achieving the high enantioselectivity as well as for activating the heteroarene substrate.</jats:p>

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