19643-70-0Relevant articles and documents
Tuning the peri effect for enantioselectivity: Asymmetric hydrogenation of unfunctionalized olefins with the BIPI ligands
Busacca, Carl A.,Qu, Bo,Gret, Nicole,Fandrick, Keith R.,Saha, Anjan K.,Marsini, Maurice,Reeves, Diana,Haddad, Nizar,Eriksson, Magnus,Wu, Jiang-Ping,Grinberg, Nelu,Lee, Heewon,Li, Zhibin,Lu, Bruce,Chen, Dajun,Hong, Yaping,Ma, Shengli,Senanayake, Chris H.
, p. 1455 - 1463 (2013)
The modular nature of the BIPI ligands allows for systematic optimization of each ligand region. The development of ligands optimized for asymmetric hydrogenation of the challenging unfunctionalized olefin substrate class is described. The naphthyl peri p
Monohydride-Dichloro Rhodium(III) Complexes with Chiral Diphosphine Ligands as Catalysts for Asymmetric Hydrogenation of Olefinic Substrates
Higashida, Kosuke,Brüning, Fabian,Tsujimoto, Nagataka,Higashihara, Kenya,Nagae, Haruki,Togni, Antonio,Mashima, Kazushi
supporting information, p. 8749 - 8759 (2020/07/04)
We report full details of the synthesis and characterization of monohydride-dichloro rhodium(III) complexes bearing chiral diphosphine ligands, such as (S)-BINAP, (S)-DM-SEGPHOS, and (S)-DTBM-SEGPHOS, producing cationic triply chloride bridged dinuclear rhodium(III) complexes (1 a: (S)-BINAP; 1 b: (S)-DM-SEGPHOS) and a neutral mononuclear monohydride-dichloro rhodium(III) complex (1 c: (S)-DTBM-SEGPHOS) in high yield and high purity. Their solid state structure and solution behavior were determined by crystallographic studies as well as full spectral data, including DOSY NMR spectroscopy. Among these three complexes, 1 c has a rigid pocket surrounded by two chloride atoms bound to the rhodium atom together with one tBu group of (S)-DTBM-SEGPHOS for fitting to simple olefins without any coordinating functional groups. Complex 1 c exhibited superior catalytic activity and enantioselectivity for asymmetric hydrogenation of exo-olefins and olefinic substrates. The catalytic activity of 1 c was compared with that of well-demonstrated dihydride species derived in situ from rhodium(I) precursors such as [Rh(cod)Cl]2 and [Rh(cod)2]+[BF4]? upon mixing with (S)-DTBM-SEGPHOS under dihydrogen.
Improved synthesis of cyclohexane-backbone iridium-complexes of quinoline-phosphine and their applications in asymmetric hydrogenation
Liu, Qibin
, (2020/09/15)
– The iridium-complexes 3 and 4 with cyclohexane-backbone derived from quinoline were easily synthesized. The key step is cis/trans stereoselective reduction of 2-(quinolin-2-yl)cyclohexanone 5 to trans-2-(quinolin-2-yl)cyclohexanol 6 using Al(Oi-Pr)3/i-P