Article
Chemistry, Organic
Xiu-Qin Dong, Xuanliang Yang, Gang Liu, Xun Xiang, Dezheng Xie, Jinyu Han, Zhengyu Han
Summary: Efficient Ni/(S,S)-Ph-BPE-catalyzed asymmetric hydrogenation of alpha-substituted alpha,beta-unsaturated phosphine oxides/phosphonates/phosphoric acids has been successfully developed, and a wide range of chiral alpha-substituted phosphine hydrogenation products were obtained in generally high yields with excellent enantioselective control (92%-99% yields, 84%->99% ee). This method features a cheap transition metal nickel catalytic system, high functional group tolerance, wide substrate scope generality, and excellent enantioselectivity. A plausible catalytic cycle was proposed for this asymmetric hydrogenation according to the results of deuterium-labeling experiments.
Article
Chemistry, Physical
Christophe M. Saudan, Aurelien Berrocosa, Julie Quintaine, Stephanie Spoehrle, Laurent Maggi, Herve Mosimann, Lionel Saudan
Summary: This paper reports a method for the regio- and chemoselective hydrogenation of conjugated dienals using a large bite-angle diphosphine and a neutral rhodium complex catalyst in the presence of a weak base. This method offers high selectivity, mild reaction conditions, and a neutral alternative to the commonly employed Claisen rearrangement for the synthesis of γ,δ-unsaturated aldehydes.
Article
Chemistry, Organic
Xixia Tang, Lu Qian, Guixia Liu, Zheng Huang
Summary: Asymmetric transfer hydrogenation of 1-aryl-1-alkylethenes with ethanol using a chiral (PCN)Ir complex as the precatalyst has been developed, demonstrating high enantioselectivities, good functional group tolerance, and operational simplicity. This method is also applied to formal intramolecular asymmetric transfer hydrogenation of alkenols without an external H-donor, allowing for the production of a tertiary stereocenter and remote ketone group simultaneously. The utility of the catalytic system is highlighted by gram scale synthesis and the synthesis of the key precursor of (R)-xanthorrhizol.
Review
Chemistry, Organic
Anirban Sen, Samir H. Chikkali
Summary: This article assesses the potential use of C-1-symmetric diphosphorus ligands in producing chiral compounds through asymmetric hydrogenation, summarizing recent strategies and advancements in metal-catalyzed asymmetric hydrogenation using these ligands. It discusses the potential of diphosphorus ligands in producing pharmaceutical intermediates, bioactive molecules, drug molecules, agrochemicals, and fragrances.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2021)
Article
Chemistry, Organic
Huifang Song, Yuli Sun, Chengrong Lu, Bei Zhao
Summary: Chiral dinuclear rare-earth metal complexes were synthesized and three unknown complexes were characterized. These chiral complexes showed high reactivity in the asymmetric hydrophosphonylation reaction, with complex 7 and chiral diamine proving to be the optimal catalyst combination. The reaction yielded hydrophosphonylation products with high yields and excellent enantiomeric excess values.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Guillaume Force, Robert J. J. Mayer, Marie Vayer, David Leboeuf
Summary: Chiral naphthalene diimide ligands (NDIPhos) were utilized in rhodium-catalyzed enantioselective hydrogenation, where these ligands' key feature is their self-assembly ability through pi-pi interactions to mimic bidentate ligands, offering an alternative to traditional supramolecular strategies. This concept was further supported by calculations using the composite electronic structure method r(2)SCAN-3c.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Organic
Chaoqiong Wang, Fang Xie, Qianling Guo, Chaochao Xie, Guofu Zi, Weiping Ye, Zhangtao Zhou, Guohua Hou, Zhanbin Zhang
Summary: The first asymmetric hydrogenation of beta,beta-diaryl unsaturated phosphonates has been achieved with excellent enantioselectivities using the Rh-(R, R)-f-spiroPhos complex as catalyst. This method also shows comparable performance for beta-aryl-beta-alkyl unsaturated phosphonates, providing chiral phosphonates with high ee values. This new methodology offers a straightforward approach to asymmetric synthesis of chiral phosphonates.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Yu Nie, Qianjia Yuan, Feng Gao, Masahiro Terada, Wanbin Zhang
Summary: An efficient iridium-catalyzed double asymmetric hydrogenation of 2,5-dialkylienecyclopentanones is reported, delivering chiral 2,5-disubstituted cyclopentanones in excellent yields and stereoselectivities. The results suggest that the two C=C bonds were hydrogenated in a stepwise manner and the second stereocenter was controlled by the chiral catalyst and the chirality of monohydrogenated product. The hydrogenated products can be prepared on a gram-scale and are easily derivatized.
Article
Chemistry, Organic
Yu Nie, Qianjia Yuan, Feng Gao, Masahiro Terada, Wanbin Zhang
Summary: Herein, we report an efficient iridium-catalyzed double asymmetric hydrogenation of 2,5-dialkylienecyclopentanones, delivering the chiral 2,5-disubstituted cyclopentanones in excellent yields and stereoselectivities. The results of the kinetic experiments and control experiments indicated that the two C=C bonds were hydrogenated in a stepwise manner and the second stereocenter was synergistically controlled by the chiral catalyst and the chirality of monohydrogenated product. The hydrogenated products can be prepared on a gram-scale and are easily derivatized.
Article
Chemistry, Inorganic & Nuclear
Nora Jannsen, Christian Fischer, Carmen Selle, Cornelia Pribbenow, Hans-Joachim Drexler, Fabian Reiss, Torsten Beweries, Detlef Heller
Summary: In this study, we systematically investigate and quantify the influence of solvent coordination on reactions of cationic rhodium(i) diphosphine complexes. We propose a method to analyze and quantify solvent binding using MeCN as a replacement for diolefins. By using UV-vis and P-31{H-1} NMR spectroscopy, we determine and compare stability constants of different complexes, and discuss the impact of different ligands and reaction temperature. DFT study reveals the relationship between stability and thermodynamics of the exchange reaction. Additionally, variable temperature NMR spectroscopy confirms the existence of a mixed solvate complex as an intermediate in the MeCN-MeOH exchange.
DALTON TRANSACTIONS
(2022)
Article
Chemistry, Organic
Rongrong Xie, Cungang Liu, Renwei Lin, Runchen Zhang, Haizhou Huang, Mingxin Chang
Summary: The strong coordination between 1,2-diamines and transition metals can hinder or disrupt regular catalytic cycles. In this study, we employed sets of additives to ensure a smooth transformation catalyzed by rhodium complexes and versatile phosphoramidite-phosphine ligands. The tunability of the ligands was fully utilized to accommodate various diamines and alpha-ketoesters for the efficient synthesis of chiral 3,4-dihydroquinox-alinones.
Article
Multidisciplinary Sciences
Zitong Wu, Wenji Wang, Haodong Guo, Guorui Gao, Haizhou Huang, Mingxin Chang
Summary: Direct asymmetric reductive amination is an efficient method for obtaining chiral amines. In this study, the authors demonstrate how primary alkyl amines can undergo this transformation in the presence of an iridium catalyst with sterically tuneable chiral phosphoramidite ligands, leading to the synthesis of pharmaceutical compounds.
NATURE COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Peng Lu, Hongliang Wang, Yihui Mao, Xin Hong, Zhan Lu
Summary: Investigation on asymmetric hydrogenation of olefins is vital for the synthesis of pharmaceutical molecules and chemical industry. A cobalt-catalyzed enantioconvergent hydrogenation method has been developed for common minimally functionalized E/Z-olefin mixtures.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Review
Chemistry, Multidisciplinary
Fan Yang, Jian-Hua Xie, Qi-Lin Zhou
Summary: Catalytic asymmetric hydrogenation is a reliable, powerful, and environmentally friendly method for synthesizing chiral molecules. Our recent studies have shown that the design and synthesis of chiral catalysts can greatly improve the efficiency and selectivity of hydrogenation reactions. By adding additional coordinating groups, the stability and efficiency of the catalyst can be significantly increased.
ACCOUNTS OF CHEMICAL RESEARCH
(2023)
Article
Chemistry, Organic
Yi-Fan Wang, Yu-Han He, Yan Su, Yang Ji, Rui Li
Summary: In this study, a palladium complex coordinated with a chiral SIPHOS ligand was evaluated as an efficient catalyst for asymmetric hydrosilylation reaction. The results showed that good to excellent enantioselectivities could be obtained in the hydrosilylation reaction of 1-aryl-2-silyl ethanols with selectively converted trichlorosilyl groups. Additionally, stable and high-yielding 1,2-bis(silyl) chiral compounds could be produced through the asymmetric hydrosilylation of beta-silyl styrenes followed by methylation of the trichlorosilyl group.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
