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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
Affiliation  

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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