1604008-08-3Relevant articles and documents
Chiral bidentate nitrogen phosphine ligand Rong-Phos iridium complex and high-enantioselectivity construction and application of nitrogen chiral center thereof
-
Paragraph 0190-0201, (2020/08/17)
The invention discloses a chiral bidentate nitrogen phosphine ligand Rong-Phos iridium complex shown as a formula (2) and a high-enantioselectivity construction method and application and applicationof a nitrogen chiral center thereof. The iridium complex has a carbon chiral center and a nitrogen chiral center at the same time and is stable in property. According to the invention, a method for high-enantioselectivity construction of the nitrogen atom center of the iridium complex is adopted, and a pair of diastereoisomer catalysts, with different nitrogen center chirality, of the iridium complexes are applied to asymmetric hydrogenation reactions of cyclic unsaturated carbonyl compounds; and the iridium complex also has excellent reaction activity and enantioselectivity in asymmetric hydrogenation reactions of other cyclic unsaturated carbonyl compounds, and the iridium complex remarkable and excellent effect and shows scientific research value and wide application prospects.
SpinPhox/iridium(I)-catalyzed asymmetric hydrogenation of cyclic α-alkylidene carbonyl compounds
Liu, Xu,Han, Zhaobin,Wang, Zheng,Ding, Kuiling
supporting information, p. 1978 - 1982 (2014/03/21)
Optically active medium-sized cyclic carbonyl compounds bearing an α-chiral carbon center are of interest in pharmaceutical sciences and asymmetric synthesis. Herein, SpinPhox/IrI catalysts have been demonstrated to be highly enantioselective in the asymmetric hydrogenation of the Ci￡C bonds in the exocyclic α,β-unsaturated cyclic carbonyls, including a broad range of α-alkylidene lactams, unsaturated cyclic ketones, and lactones. It is noteworthy that the procedure can be successfully used in the asymmetric hydrogenation of the challenging α-alkylidenelactam substrates with six- or seven-membered rings, thus affording the corresponding optically active carbonyl compounds with an α-chiral carbon center in generally excellent enantiomeric excesses (up to 98 % ee). Synthetic utility of the protocol has also been demonstrated in the asymmetric synthesis of the anti-inflammatory drug loxoprofen and its analogue, as well as biologically important ε-aminocaproic acid derivatives. Take it for a spin: SpinPhox/IrI complexes are highly efficient and versatile in the enantioselective hydrogenation of a broad spectrum of exocyclic α,β-unsaturated carbonyl compounds, especially the challenging α-alkylidene lactam substrates with six- or seven-membered rings. The synthetic utility of the present protocol is demonstrated in the asymmetric synthesis of biologically important loxoprofen and ε-aminocaproic acid derivatives. Copyright
