Readily Available Phosphine−Phosphoramidite Ligands for Highly Efficient Rh-Catalyzed Enantioselective Hydrogenations

Huang, Jia‐Di; Hu, Xiang‐Ping; Duan, Zheng-Chao; Zeng, Qing-Hen; Yu, Sijie; Deng, Jun; Wang, Daoyong; Zheng, Zhuo

doi:10.1021/ol0617749

Cited by 74 publications

(21 citation statements)

References 15 publications

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“…Compound 1, which contained a chiral primary amine motif as a building block for the hexadentate ligand, was easily prepared from (S)-1-phenylethanamine in moderate yield (Scheme 1). [9] Simultaneously, two different chiral aldehydes, 3-hydroxy-4-(2-hydroxynaphthalen-1-yl)-2-naphthaldehyde and bi-2-hydroxy-3-naphthaldehyde, were prepared from chiral BINOL in high yields (Scheme 2). [10] Then the five similar ligands (L1-L5) that contained both axial and sp 3 -central chirality were prepared by Schiff base condensation of chiral primary-amine-based phosphine ligand 1 and different BINOL-derived aldehydes (2 a or 3 a, 50-62 % total isolated yield; also see the Supporting Information).…”

Section: Synthesis Of Multidentate and Multifunctional Phosphine Ligandsmentioning

confidence: 99%

Modulation of Multifunctional N,O,P Ligands for Enantioselective Copper‐Catalyzed Conjugate Addition of Diethylzinc and Trapping of the Zinc Enolate

Ye¹,

Zheng²,

Deng³

et al. 2013

Chemistry An Asian Journal

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In this work, we have successfully synthesized a new family of chiral Schiff base–phosphine ligands derived from chiral binaphthol (BINOL) and chiral primary amine. The controllable synthesis of a novel hexadentate and tetradentate N,O,P ligand that contains both axial and sp3-central chirality from axial BINOL and sp3-central primary amine led to the establishment of an efficient multifunctional N,O,P ligand for copper-catalyzed conjugate addition of an organozinc reagent. In the asymmetric conjugate reaction of organozinc reagents to enones, the polymer-like bimetallic multinuclear Cu-Zn complex constructed in situ was found to be substrate-selective and a highly excellent catalyst for diethylzinc reagents in terms of enantioselectivity (up to >99 % ee). More importantly, the chirality matching between different chiral sources, C2-axial binaphthol and sp3-central chiral phosphine, was crucial to the enantioselective induction in this reaction. The experimental results indicated that our chiral ligand (R,S,S)-L1- and (R,S)-L4-based bimetallic complex catalyst system exhibited the highest catalytic performance to date in terms of enantioselectivity and conversion even in the presence of 0.005 mol % of catalyst (S/C = 20 000, turnover number (TON) = 17,600). We also studied the tandem silylation or acylation of enantiomerically enriched zinc enolates that formed in situ from copper-L4-complex-catalyzed conjugate addition, which resulted in the high-yield synthesis of chiral silyl enol ethers and enoacetates, respectively. Furthermore, the specialized structure of the present multifunctional N,O,P ligand L1 or L4, and the corresponding mechanistic study of the copper catalyst system were investigated by 31P NMR spectroscopy, circular dichroism (CD), and UV/Vis absorption.

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Section: Synthesis Of Multidentate and Multifunctional Phosphine Ligandsmentioning

confidence: 99%

Modulation of Multifunctional N,O,P Ligands for Enantioselective Copper‐Catalyzed Conjugate Addition of Diethylzinc and Trapping of the Zinc Enolate

Ye¹,

Zheng²,

Deng³

et al. 2013

Chemistry An Asian Journal

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“…Considering the structural similarity between 1-ferrocenylethylamine and 1-phenylethylamine and low cost of chiral 1-phenylethylamine, we then surmised that 1-phenylethylamine-derived phosphine-phosphoramidite ligand (abbreviated as PEAPhos, 36) may be a good alternative to ferrocene-based PPFAPhos ligands [26].…”

Section: Chiral Monodentate Phosphorus-containing Ligands For Catalytmentioning

confidence: 99%

Adventure in Asymmetric Hydrogenation: Synthesis of Chiral Phosphorus Ligands and Asymmetric Hydrogenation of Heteroaromatics

Wang

et al. 2011

Asymmetric Catalysis From a Chinese Perspective

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Catalytic asymmetric hydrogenations of prochiral unsaturated compounds, such as olefins, ketones, and imines, have been intensively studied and are considered as a versatile method of the synthesis of chiral compounds due to atom economy and operational simplicity. Since 2002, we mainly focused on synthesis of new phosphorus ligands, asymmetric hydrogenation of heteroaromatic compounds and palladium-catalyzed asymmetric hydrogenation. Significant contribution was made in the Dalian Institute of Chemical Physics. In this chapter, we hope to share our experience and adventure in the development of chiral monophosphite ligands and phosphine-phosphoramidite ligands, asymmetric hydrogenation of heteroaromatic compounds, and the development of new homogeneous palladium catalytic hydrogenation system, which have a wide range of applications in synthesis of chiral compounds.

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“…Although high efficiency of PPFAPhos is observed in the Rh-catalyzed asymmetric hydrogenation of various enamides, high cost in the tedious synthesis of this ligand class has seriously prevented its practical application in asymmetric catalysis. To overcome this shortcoming, in 2006, we developed a new class of phosphinephosphoramidite ligands, PEAPhos (45), bearing a similar structure to PPFAPhos (Figure 9.11) [48]. PEAPhos can be easily prepared from commercially available and inexpensive (S)-a-phenylethylamine through a two-step transformation.…”

Section: Unsymmetrical Hybrid Phosphorus-containing Ligands For Rh-camentioning

confidence: 99%

Bidentate Ligands for Enantioselective Enamide Reduction

Zheng

2010

Chiral Amine Synthesis

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Scheme 9.1 The first catalytic asymmetric hydrogenation of enamide 1a reported by Kagan.Scheme 9.2 General methods for the synthesis of N-acyl-a-arylenamides. 274j 9 Bidentate Ligands for Enantioselective Enamide Reduction R O Scheme 9.4 Synthesis of exocyclic enamides. 9.2 Catalytic Enantioselective Hydrogenation of Enamides j275 4 15 Scheme 9.11 Rh-catalyzed asymmetric hydrogenation of ortho-substituted arylenamides with a triphosphorus bidentate phosphine-phosphoramidite ligand 49. 288j 9 Bidentate Ligands for Enantioselective Enamide Reduction P P P P Me-DuPhos Me-BPE 61 Scheme 9.15 Asymmetric hydrogenation of tetra-substituted cyclic enamides using the Ru-catalyst containing Me-DuPHOS or Me-BPE. 9.2 Catalytic Enantioselective Hydrogenation of Enamides j291

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Readily Available Phosphine−Phosphoramidite Ligands for Highly Efficient Rh-Catalyzed Enantioselective Hydrogenations

Cited by 74 publications

References 15 publications

Modulation of Multifunctional N,O,P Ligands for Enantioselective Copper‐Catalyzed Conjugate Addition of Diethylzinc and Trapping of the Zinc Enolate

Modulation of Multifunctional N,O,P Ligands for Enantioselective Copper‐Catalyzed Conjugate Addition of Diethylzinc and Trapping of the Zinc Enolate

Adventure in Asymmetric Hydrogenation: Synthesis of Chiral Phosphorus Ligands and Asymmetric Hydrogenation of Heteroaromatics

Bidentate Ligands for Enantioselective Enamide Reduction

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