Asymmetric Hydrogenation of Polysubstituted Aromatic Ketones Catalyzed by the DIPSkewphos/PICA Derivative–Ruthenium(II) Complexes,ChemCatChem

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Asymmetric Hydrogenation of Polysubstituted Aromatic Ketones Catalyzed by the DIPSkewphos/PICA Derivative–Ruthenium(II) Complexes
ChemCatChem ( IF 3.8 ) Pub Date : 2018-07-22 , DOI: 10.1002/cctc.201800848
Noriyuki Utsumi ₁ , Noriyoshi Arai ₂ , Kei Kawaguchi ₂ , Takeaki Katayama ₁ , Toshihisa Yasuda ₁ , Kunihiko Murata ₁ , Takeshi Ohkuma ₂

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The DIPSkewphos/PICA derivative‐Ru(II) complexes catalyzed asymmetric hydrogenation of significantly sterically hindered 2’,3’,4’,5’,6’‐pentamethylacetophenone, which was not reduced with NaBH₄ at 25 °C, with a substrate‐to‐catalyst molar ratio (S/C) of 2000 under 50 atm of H₂ in a base‐containing 2‐propanol to afford the alcohol in 99 % ee quantitatively. A series of polysubstituted aromatic ketones was smoothly reacted with an S/C of 300–10,000 under 10–50 atm of H₂, yielding the alcoholic products in up to 99 % ee. The catalyst system achieved an industrial‐scale (50 kg) hydrogenation of 2’,6’‐dichloro‐3’‐fluoroacetophenone, affording the alcohol in 96 % isolated yield and in 98 % ee. The obtained alcoholic product is known as a key intermediate for the synthesis of the medicine crizotinib.

中文翻译：

DIPSkewphos / PICA衍生物-钌（II）配合物催化的多取代芳族酮的不对称加氢反应

DIPSkewphos / PICA衍生物-Ru（II）配合物催化具有明显空间位阻的2'，3'，4'，5'，6'-五甲基苯乙酮的不对称氢化反应，在25°C下使用NaBH ₄不会还原该反应，并具有底物在含碱的2-丙醇中，H ₂在50个大气压下的催化剂与催化剂的摩尔比（S / C）为2000，以定量方式提供99％ee的醇。在H _2的10-50 atm下，一系列多取代的芳族酮与300 / 10,000的S / C平稳反应，生成的醇类产品的ee高达99％。该催化剂体系实现了2'，6'-二氯-3'-氟苯乙酮的工业规模加氢（50 kg），分离出的乙醇产率为96％，ee为98％。所获得的醇产物被称为合成克唑替尼的关键中间体。

更新日期：2018-07-22

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