A Novel Class of P−O Monophosphite Ligands Derived from <scp>d</scp>-Mannitol:  Broad Applications in Highly Enantioselective Rh-Catalyzed Hydrogenations

Huang, Hanmin; Zheng, Zhuo; Luo, Huili; Bai, Changmin; Hu, Xinquan; Chen, Huilin

doi:10.1021/jo035627p

Cited by 62 publications

(32 citation statements)

References 20 publications

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“…utility of this notion and enhance the versatility of this ligand type in asymmetric reactions, in 2004, we developed a new class of chiral monophosphite ligands, ManniPhos 7 ( Fig. 2) [12], based on d-mannitol. These new ligands contain an extra chiral scaffold with a fair degree of rigidity and flexibility in attaching additional groups in a proper spatial configuration such that the ligands may not only offer the effect of additional groups but also act like hemilabile ligands to enhance the enantioselectivity.…”

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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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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“…The rhodium catalyst containing a phosphite 29 was also efficient for the asymmetric hydrogenation of Z/E mixture of b-substituted arylenamide 15a, providing N-acetyl arylamine 16a with 96.7% ee (Scheme 8.11). The D-mannitol-based monophosphite 30 (ManniPhos) was found to be excellent ligand in the asymmetric hydrogenation of a-arylenamides [38].…”

Section: Chiral Monodentate Phosphite Ligandsmentioning

confidence: 99%

Enantioselective Hydrogenation of Enamines with Monodentate Phosphorus Ligands

Zhou

Xie

2010

Chiral Amine Synthesis

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Chiral amines are widely used as chiral ligands, auxiliaries, resolving agents, and important intermediates in synthetic chemistry. Asymmetric hydrogenation of enamines such as enamides is an atom economic and straightforward protocol for the preparation of chiral amines. In 1972, Kagan reported the first example of asymmetric hydrogenation of enamides with chiral Rh-DIOP complex as a catalyst [1]. This opened a new window for the asymmetric synthesis of chiral N-acyl amines although the enantioselectivity of the reaction was not more than 78% ee (Scheme 8.1). When Noyori et al. introduced chiral Ru-BINAP, it significantly increased the level of enantioselectivity to 99.5% ee in the asymmetric hydrogenation of N-acyl-1-alkylidenetetrahydroisoquinolines [2]. However, this ruthenium-catalyzed asymmetric hydrogenation is very sensitive to the stereochemistry of the enamide, with only the (Z)-isomer of the enamide being hydrogenated while the (E)-isomer was recovered intact (Scheme 8.2). Another breakthrough in this field came in 1996 when Burk et al. showed that chiral rhodium complexes bearing a diphosphine ligand Me-DuPHOS or Me-BPE could hydrogenate a-arylenamides to yield a wide variety of valuable a-1-arylethylamine derivatives with high enantioselectivities (up to 98.5% ee) (Scheme 8.3) [3]. The merit of this hydrogenation is that both (E)-and (Z)-isomers of b-substituted enamides can be hydrogenated, thus enlarging the substrate scope of the reaction. Subsequently, many efficient diphosphines, such as BICP (bis(diphenylphosphino)dicyclopentane) [4], PennPhosP, NHAc NHAc 1 bar H 2 [RhCl(COD) 2 ] 2 /(S,S)-DIOP EtOH-C 6 H 6 (2 :1), rt 95% yield, 78% ee PPh 2 PPh 2 O O (S,S)-DIOP Scheme 8.1 Rh-DIOP catalyzed asymmetric hydrogenation of enamides.

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“…[76] The glucose-derived phosphite 31 is also well suited for Rh-catalyzed hydrogenation, especially of enol acetates 29.…”

Section: Modular Monodentate P Ligands In Combinatorial Asymmetric Trmentioning

confidence: 99%

Combinatorial Transition‐Metal Catalysis: Mixing Monodentate Ligands to Control Enantio‐, Diastereo‐, and Regioselectivity

Reetz

2008

Angew Chem Int Ed

245

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This review focuses on a new approach to combinatorial homogeneous transition-metal catalysis which goes beyond the traditional parallel preparation of modular ligands. It is based on the use of mixtures of monodentate ligands L(a) and L(b), which upon exposure to a transition metal (M) form not only the two homocombinations [ML(a)L(a)] and [ML(b)L(b)], but also the heterocombination [ML(a)L(b)]. If the latter is more reactive and selective than the homocombinations, an improved catalyst system is formed without the need to synthesize new ligands. Thus, the control of enantio,- diastereo-, and regioselectivity is possible.

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A Novel Class of P−O Monophosphite Ligands Derived from d-Mannitol: Broad Applications in Highly Enantioselective Rh-Catalyzed Hydrogenations

Cited by 62 publications

References 20 publications

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

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

Enantioselective Hydrogenation of Enamines with Monodentate Phosphorus Ligands

Combinatorial Transition‐Metal Catalysis: Mixing Monodentate Ligands to Control Enantio‐, Diastereo‐, and Regioselectivity

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