Catalytic Asymmetric Hydrogenation of Naphthalenes

Kuwano, Ryoichi; Morioka, Ryuichi; Kashiwabara, Manabu; Kameyama, Nao

doi:10.1002/anie.201201153

Cited by 104 publications

(47 citation statements)

References 45 publications

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“…(7)). 7 Methyl ester 11a failed to give the desired chiral tetralin 12a in moderate yield as well as with good enantioselectivity because of its low solubility. However, the low yield and selectivity were remarkably improved by replacing the methyl by isobutyl.…”

Section: Resultsmentioning

confidence: 99%

Catalytic Asymmetric Hydrogenation of Heteroarenes and Arenes

Kuwano

2015

Phosphorus, Sulfur, and Silicon and the Related Elements

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A trans-chelating chiral bisphosphine, PhTRAP, allows the ruthenium-catalyzed hydrogenation of various azoles to proceed with high enantioselectivity. The PhTRAP-ruthenium catalyst transformed indoles, pyrroles, imidazoles, and oxazoles into the corresponding chiral heterocycles. Naphthalenes are also reduced with hydrogen by the chiral ruthenium catalyst, exclusively giving tetralins. Some 2-alkoxytetralins were obtained with over 90% ee from the catalytic asymmetric hydrogenation of the corresponding substituted naphthalenes.

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Section: Resultsmentioning

confidence: 99%

Catalytic Asymmetric Hydrogenation of Heteroarenes and Arenes

Kuwano

2015

Phosphorus, Sulfur, and Silicon and the Related Elements

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“…However, despite multiple attempts to optimise the reaction conditions (basic additives, solvent and temperature), the enantioselectivities remained lower than 86%. 81 Disappointingly, 35 the authors were unable to hydrogenate dialkyl-substituted naphthalenes under these conditions. These results suggest that substrate coordination by binding of the R-oxy group to the ruthenium centre is required for efficient catalysis.…”

Section: Hydrogenation Of (Hetero)aromatic Compoundsmentioning

confidence: 99%

Catalytic enantioselective reductive desymmetrisation of achiral and meso compounds

et al. 2013

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Herein an overview of reductive catalytic enantioselective desymmetrisation of achiral or meso compounds is provided. The most efficient reductive desymmetrisations described in the literature, which involve the reduction of C=O, C=N, C=C and C-halogen bonds, or reductive ring-opening, are summarised. The structural diversity of the valuable highly enantioenriched intermediates prepared by reductive desymmetrisation is highlighted.

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“…

Chiral 1,2,3,4-tetrahydroisoquinolines are ubiquitous structural motifs in many natural alkaloids and biologically active compounds. [12] However, the development of the enantioselective hydrogenation of isoquinolines has met with limited success, probably owing to lower reactivity and strong coordination to the catalyst. So far, significant progress on the asymmetric hydrogenation of aromatic compounds has been implemented successfully [3] for substrates such as quinolines, [4] quinoxalines, [5] indoles, [6] pyrroles, [7] pyridines, [8] furans, [9] imidazoles, [10] thiophenes [11] and aromatic carbocyclic rings.

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Enantioselective Iridium‐Catalyzed Hydrogenation of 1‐ and 3‐Substituted Isoquinolinium Salts

et al. 2013

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Chiral 1,2,3,4-tetrahydroisoquinolines are ubiquitous structural motifs in many natural alkaloids and biologically active compounds. [1] Among the various catalytic methods developed for the construction of chiral tetrahydroisoquinolines during the past decades, [2] asymmetric hydrogenation of isoquinolines unquestionably serves as one of the most straightforward and powerful methods. So far, significant progress on the asymmetric hydrogenation of aromatic compounds has been implemented successfully [3] for substrates such as quinolines, [4] quinoxalines, [5] indoles, [6] pyrroles, [7] pyridines, [8] furans, [9] imidazoles, [10] thiophenes [11] and aromatic carbocyclic rings. [12] However, the development of the enantioselective hydrogenation of isoquinolines has met with limited success, probably owing to lower reactivity and strong coordination to the catalyst. In 2006, our group reported the first iridium-catalyzed asymmetric hydrogenation of isoquinolines, which were activated by chloroformates, with moderate enantioselectivity and yield. [13] Very recently, an enantioselective hydrogenation of 3,4-disubstituted isoquinolines employing catalyst activation was successfully described, [14] nevertheless, this strategy is not suitable for 1substituted isoquinolines. Moreover, there is no report on the asymmetric hydrogenation of 3-substituted isoquinolines heretofore. Therefore, the development of a general and efficient strategy for asymmetric hydrogenation of 1-and 3substituted isoquinolines is still a very valuable and challenging area of chemical research.Recently, our group successfully documented the iridiumcatalyzed asymmetric hydrogenation of simple pyridinium salts, which were formed by using benzyl bromide and possess higher reactivity than the corresponding pyridines. [15] As part of our ongoing efforts to promote the development of asymmetric hydrogenation of heteroaromatic compounds, [3a,b] and considering the similar structure of pyridine to isoquinoline, we envisioned that activating isoquinoline as the N-benzyl isoquinolinium salt would effectively improve the reactivity to facilitate hydrogenation (Scheme 1). Herein, we report the iridium-catalyzed asymmetric hydrogenation of 1-Scheme 3. Mechanistic investigation of the iridium-catalyzed asymmetric hydrogenation of 1-and 3-substituted isoquinolinium salts.Scheme 4. Proposed hydrogenation mechanism.Scheme 5. Synthesis of the chiral drug (+)-solifenacin. Angewandte Chemie

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Catalytic Asymmetric Hydrogenation of Naphthalenes

Cited by 104 publications

References 45 publications

Catalytic Asymmetric Hydrogenation of Heteroarenes and Arenes

Catalytic Asymmetric Hydrogenation of Heteroarenes and Arenes

Catalytic enantioselective reductive desymmetrisation of achiral and meso compounds

Enantioselective Iridium‐Catalyzed Hydrogenation of 1‐ and 3‐Substituted Isoquinolinium Salts

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