446-65-1Relevant articles and documents
Highly enantioselective construction of CF3-bearing all-carbon quaternary stereocenters: Hiral spiro-fused bisoxazoline ligands with 1,1′-binaphthyl sidearm for asymmetric Michael-type Friedel-Crafts reaction
Bao, Robert Li-Yuan,Fu, Kang,Shi, Lei
, (2021/11/27)
A novel class of chiral spiro-fused bisoxazoline ligands possessing a deep chiral pocket was prepared. The developed ligands have been employed in the nickel-catalyzed highly enantioselective Michael-type Friedel-Crafts reaction, affording the products bearing a trifluoromethylated all-carbon quaternary stereocenter with moderate to excellent yields (up to 99%) and good to excellent enantioselectivies (up to > 99.9% ee). Moreover, a proposed model of chiral pocket revealed that the attack of indole from the Re-face of β-CF3-β-disubstituted nitroalkene was favorable.
Synthesis of Unsymmetric Triarylmethanes Bearing CF 3-Substituted All-Carbon Quaternary Stereocenters: 1,6-Arylation of δ-Trifluo romethyl Substituted para -Quinone Methides
Ma, Yingang,Pang, Jingxiang,Pan, Xiaoguang,Ma, Shutao,Liu, Xigong,Liu, Lei
supporting information, p. 1619 - 1622 (2020/09/15)
Pre-synthesized δ-CF 3-δ-aryl-disubstituted para -quinone methides bearing δ-substituents were identified as isolable and storable substrates for 1,6-arylation reactions. A broad range of electron-rich arenes and heteroarenes participated in the arylation process, furnishing a wide array of unsymmetrical CF 3-substituted triarylmethanes in high efficiency. The mild and expeditious protocol exhibited broad scopes of both arene and para -quinone methide components.
Asymmetric Hydrogenation of Aryl Perfluoroalkyl Ketones Catalyzed by Rhodium(III) Monohydride Complexes Bearing Josiphos Ligands
Brüning, Fabian,Nagae, Haruki,K?ch, Daniel,Mashima, Kazushi,Togni, Antonio
supporting information, p. 10818 - 10822 (2019/07/31)
The asymmetric hydrogenation of 2,2,2-trifluoroacetophenones and aryl perfluoroalkyl ketones was developed using a unique, well-defined chloride-bridged dinuclear rhodium(III) complex bearing Josiphos-type diphosphine ligands. These complexes were prepared from [RhCl(cod)]2, Josiphos ligands, and hydrochloric acid. As catalyst precursors, they allow for the efficient and enantioselective synthesis (up to 99 % ee) of chiral secondary alcohols with perfluoroalkyl groups. This system does not require an activating base for the hydrogenation of 2,2,2-trifluoroacetophenones. Additionally, the enantioselective C=O hydrogenations of 2-phenyl-3-(haloacetyl)-indoles, a class of privileged structures in medicinal chemistry, is reported for the first time.