1944-05-4Relevant articles and documents
Transition Metal Catalyst-Free, Base-Promoted 1,2-Additions of Polyfluorophenylboronates to Aldehydes and Ketones
Budiman, Yudha P.,Friedrich, Alexandra,Kole, Goutam Kumar,Liu, Zhiqiang,Luo, Xiaoling,Marder, Todd B.,Radius, Udo,Tian, Ya-Ming,Westcott, Stephen A.
, p. 16529 - 16538 (2021/06/23)
A novel protocol for the transition metal-free 1,2-addition of polyfluoroaryl boronate esters to aldehydes and ketones is reported, which provides secondary alcohols, tertiary alcohols, and ketones. Control experiments and DFT calculations indicate that both the ortho-F substituents on the polyfluorophenyl boronates and the counterion K+ in the carbonate base are critical. The distinguishing features of this procedure include the employment of commercially available starting materials and the broad scope of the reaction with a wide variety of carbonyl compounds giving moderate to excellent yields. Intriguing structural features involving O?H???O and O?H???N hydrogen bonding, as well as arene-perfluoroarene interactions, in this series of racemic polyfluoroaryl carbinols have also been addressed.
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.
Perfluoroalkyl and -aryl Zinc Ate Complexes: Generation, Reactivity, and Synthetic Application
Wang, Xuan,Hirano, Keiichi,Kurauchi, Daisuke,Kato, Hisano,Toriumi, Naoyuki,Takita, Ryo,Uchiyama, Masanobu
supporting information, p. 10993 - 10996 (2015/11/10)
A combination of dimethylzinc, perfluoroalkyl iodide, and LiCl afforded a new type of perfluoroalkyl (RF) zinc ate complex. These complexes show much greater thermal stability than conventional perfluorinated metal species, such as RF-lithium species and Grignard reagents, and they can be used at room temperature or higher. The results of DFT calculations on the origin of the enhanced stability are reported and the synthetic utility of RF-zincate complexes is demonstrated. The magnificent ate: A combination of dimethylzinc, perfluoroalkyl iodide, and LiCl afforded a new type of perfluoroalkyl (RF) zinc ate complex. These complexes show greater thermal stability than conventional perfluorinated metal species and they can be used at room temperature or higher. The results of DFT calculations on the origin of the enhanced stability are reported and the synthetic utility of RF-zincate complexes is demonstrated.
