open access

https://hdl.handle.net/2115/75497

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

英語

ruthenium

2018-09-20

Wiley-Blackwell

ChemCatChem

10(18)

3955-3959

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 degrees C, with a substrate-to-catalyst molar ratio (S/C) of 2000 under 50 atm of H-2 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 H-2, 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.

学術雑誌論文

Accepted Manuscript

This is the peer reviewed version of the following article: ChemCatChem 10 (18) 3955-3959 2018-09-20, which has been published in final form at http://doi.org/10.1002/cctc.201800848. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving.

1867-3880