Catalytic asymmetric hydrogenation of indoles using a rhodium complex with a chiral bisphosphine ligand PhTRAP

The methodological development of a series of domino or cascade reactions affording a series of N‐heterocycles is described. The rapid formation of these ring systems is in each case associated with the incorporation of a Heck reaction at either an early or a late stage of the domino process. A range of catalytic conditions and substrate modifications for optimisation of domino Tsuji–Trost/Heck, Buchwald–Hartwig/Heck and Heck/carbopalladation reaction sequences are reported.

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“…Spectroscopic data for this sample were consistent with those described in the literature. [56] Selected Reaction Procedures for Table 1 …”

Section: Methodsmentioning

confidence: 99%

The Development of Domino Reactions Incorporating the Heck Reaction: The Formation of N‐Heterocycles

et al. 2011

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“…The PhTRAP-rhodium catalyst showed high enantioselectivity for the hydrogenation of N-Boc or Ac-protected 2-substituted indoles, for Ac-protected 3-substituted indole, the above catalytic system gave the major undesirable alcoholysis product. In 2004, they used Ts as protecting group of 3-substituted indoles to yield the products with high enantioselectivities and conversions [103]. [104].…”

Section: Asymmetric Hydrogenation Of Indoles Pyrroles and Furansmentioning

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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“…Though the asymmetric hydrogenation of 2-and 3-substituted indoles with N-acetyl and N-tosyl as protective groups, respectively, has achieved great progress [38], there still exist some challenging task such as changing the protecting group and the reduction of 2,3-disubstituted indoles. Compared to the former protecting groups, tert-butoxycarbonyl is more readily attached to the indoles and removed from the products.…”

Section: Asymmetric Hydrogenation Of Indolesmentioning

confidence: 99%

Enantioselective Reduction of Nitrogen‐Based Heteroaromatic Compounds

Wang

Zhou

Wang

2010

Chiral Amine Synthesis

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Optically active amines are fundamentally important synthetic intermediates and structural components of biologically active natural products, drugs, and pharmaceuticals. Asymmetric hydrogenation of nitrogen-based heteroaromatic compounds is one of the most attractive and efficient approaches to enantiomerically pure amines, especially for numerous saturated or partially saturated chiral cyclic amines, whose synthesis by direct cyclization is often difficult. In the past decades, some progresses have been achieved in the hydrogenation of nitrogen-containing heteroaromatic compounds [1]. For example, quinolines, quinoxalines, pyridines, indoles, and pyrroles have been hydrogenated successfully with over 90% enantiomeric excess (ee). In this chapter, we focus on the synthesis of chiral amines via enantioselective hydrogenation of nitrogen-based heteroaromatic compounds. Asymmetric Hydrogenation of Quinolines Ir-and Ru-Catalyzed Asymmetric Hydrogenation of QuinolinesAmong these studies on asymmetric hydrogenation of nitrogen-based heteroaromatic compounds, the hydrogenation of quinolines was studied extensively and elaborately. In 2003, Zhou and coworkers reported the first highly enantioselective hydrogenation of quinolines with high enantioselectivities [2]. They employed [Ir(COD)Cl] 2 /MeO-BiPhep as catalyst using iodine as additive, while the hydrogenation reaction could not take place in the absence of iodine. Their studies showed that this reaction was highly solvent dependent, and toluene was the best solvent.Subsequently, some commercially available chiral bidentate phosphine ligands were tested for the asymmetric hydrogenation of quinolines, and (S)-MeO-BiPhep was the best ligand with 94% ee (Scheme 10.1). The optimal conditions are [Ir(COD) Cl] 2 /MeO-BiPhep/I 2 in toluene at 700 psi H 2 .

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Catalytic asymmetric hydrogenation of indoles using a rhodium complex with a chiral bisphosphine ligand PhTRAP

Cited by 114 publications

References 39 publications

The Development of Domino Reactions Incorporating the Heck Reaction: The Formation of N‐Heterocycles

The Development of Domino Reactions Incorporating the Heck Reaction: The Formation of N‐Heterocycles

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

Enantioselective Reduction of Nitrogen‐Based Heteroaromatic Compounds

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