Development of Ferrocene-Based Diamine-Phosphine-Sulfonamide Ligands for Iridium-Catalyzed Asymmetric Hydrogenation of Ketones

Ling, Fei; Nian, Sanfei; Chen, Jiachen; Luo, Wenjun; Wang, Ze; Lv, Yaping; Zhong, Weihui

doi:10.1021/acs.joc.8b01276

Cited by 66 publications

(27 citation statements)

References 56 publications

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“…10 To date, many chemical catalysts have been used for asymmetric reduction of 1-tetralone (1) and its derivatives, such as iridiumcatalyzed ligands, oxazaborolidine, amino acid-based ligands, and lutidine-based ligands. [11][12][13][14][15] In the literature, various chemical catalysts were tested for asymmetric reduction of substrate 1. However, to our knowledge, the use of biocatalyst for reduction of 1 has limited.…”

Section: Introductionmentioning

confidence: 99%

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Biocatalytic asymmetric synthesis of (R)‐1‐tetralol using Lactobacillus paracasei BD101

Kalay

Şahin

2021

Chirality

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Asymmetric bioreduction of ketones is a fundamental process in the production of organic molecules. Compounds containing tetralone rings are found in the structure of many biologically active and pharmaceutical molecules. Biocatalytic reduction of ketones is one of the most promising and significant routes to prepare optically active alcohols. In this study, the reductive capacity of Lactobacillus paracasei BD101 was investigated as whole-cell biocatalyst in the enantioselective reduction of 1-tetralone (1). In biocatalytic reduction reactions, the conversion of the substrate and the enantiomeric excess (ee) of the product are significantly affected by optimization parameters such as temperature, agitation rate, pH, and incubation time. Effects of these parameters on ee and conversion were investigated comprehensively. (R)-1-tetralol ((R)-2), which can be used to treat disorder such as obsessive compulsive, posttraumatic stress, premenstrual dysphoric, and social anxiety, was manufactured in enantiopure form, high yield and gram-scale, using whole-cell biocatalysts of L. paracasei BD101. The 7.04 g of (R)-2 was obtained in optically pure form with 95% yield. Also, to our knowledge, this is the first report on production of (R)-2 using whole-cell biocatalyst in excellent yield, conversion, enantiopure form and gram scale. This is a clean, eco-friendly and cheap method for the synthesis of (R)-2 compared with chemical catalyst.

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Section: Introductionmentioning

confidence: 99%

“…These products containing tetralone ring are of great interest in the drug industry 10 . To date, many chemical catalysts have been used for asymmetric reduction of 1‐tetralone ( 1) and its derivatives, such as iridium‐catalyzed ligands, oxazaborolidine, amino acid‐based ligands, and lutidine‐based ligands 11–15 …”

Section: Introductionmentioning

confidence: 99%

Biocatalytic asymmetric synthesis of (R)‐1‐tetralol using Lactobacillus paracasei BD101

Kalay

Şahin

2021

Chirality

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“…Thus, it is important to develop enantioselective green methods for the reduction of 1‐(benzofuran‐2‐yl)ethanone to the corresponding chiral alcohols. For instance, Zhong and coworkers have improved a series of tridentate ferrocene‐based diamine‐phosphine sulfonamide ligands and applied them in the asymmetric reduction of ketones, affording ( R )‐benzofuran alcohol with a 98% enantiomeric excess (ee) and a 99% yield . Lu and coworkers demonstrated cobalt‐catalyzed asymmetric hydrogenation of 1‐(benzofuran‐2‐yl)ethanone with 93% ee using the chiral iminophenyl oxazolinylphenyl amines ligands .…”

Section: Introductionmentioning

confidence: 99%

Green synthesis of enantiopure (S)‐1‐(benzofuran‐2‐yl)ethanol by whole‐cell biocatalyst

Şahin

2019

Chirality

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Optically active aromatic alcohols are valuable chiral building blocks of many natural products and chiral drugs. Lactobacillus paracasei BD87E6, which was isolated from a cereal-based fermented beverage, was shown as a biocatalyst for the bioreduction of 1-(benzofuran-2-yl) ethanone to (S)-1-(benzofuran-2-yl) ethanol with highly stereoselectivity. The bioreduction conditions were optimized using L. paracasei BD87E6 to obtain high enantiomeric excess (ee) and conversion. After optimization of the bioreduction conditions, it was shown that the bioreduction of 1-(benzofuran-2-yl)ethanone was performed in mild reaction conditions. The asymmetric bioreduction of the 1-(benzofuran-2-yl)ethanone had reached 92% yield with ee of higher than 99.9% at 6.73 g of substrate. Our study gave the first example for enantiopure production of (S)-1-(benzofuran-2-yl)ethanol by a biological green method.This process is also scalable and has potential in application. In this study, a basic and novel whole-cell mediated biocatalytic method was performed for the enantiopure production of (S)-1-(benzofuran-2-yl)ethanol in the aqueous medium, which empowered the synthesis of a precious chiral intermediary process to be converted into a sophisticated molecule for drug production. KEYWORDS (S)-1-(benzofuran-2-yl)ethanol, asymmetric bioreduction, chirality, Lactobacillus paracasei BD87E6, whole-cell biocatalysts

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“…[14] In 2017, Shi et al developed Pd(0)/chiral phosphoric acid cocatalyzed α-arylation of pyrazol-5-ones with 2-indolylmethanols afforded the αarylation products of pyrazol-5-ones in generally high yields with good enantioselectivities (Scheme 1a). [16] Inspired by our previous work on developing chiral bifunctional ferrocenylphosphine catalysts, [17] we become interested in applying our designed catalysts in asymmetric synthesis of chiral pyrazolone derivatives by treatment of MBH carbonates with pyrazolones. The limited example was reported by Lu, disclosing the chiral amino acid derived phosphine catalyzed asymmetric cyclization of pyazolones and β'-acetate allene, affording spiropyrazole derivatives in high yields with good enantioselectivities (Scheme 1b).…”

Section: Introductionmentioning

confidence: 99%

Chiral Bifunctional Ferrocenylphosphine‐Catalyzed Enantioselective Allylic Alkylation of Morita−Baylis−Hillman Carbonates with Pyrazolin‐5‐ones

et al. 2018

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A chiral bifunctional ferrocenylphosphine catalyzed asymmetric allylic alkylation of MoritaÀ BaylisÀ Hillman (MBH) carbonates with pyrazolin-5-ones was developed. The reaction afforded the desired pyrazolone derivatives in moderate to good yields (up to 80%), and with high enantioselectivities (up to 98% ee). Figure 1. Biologically active pyrazolone derivatives. Scheme 1. Pyrazolin-5-one as nucleophilic reagent in asymmetrical transformations.

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Development of Ferrocene-Based Diamine-Phosphine-Sulfonamide Ligands for Iridium-Catalyzed Asymmetric Hydrogenation of Ketones

Cited by 66 publications

References 56 publications

Biocatalytic asymmetric synthesis of (R)‐1‐tetralol using Lactobacillus paracasei BD101

Biocatalytic asymmetric synthesis of (R)‐1‐tetralol using Lactobacillus paracasei BD101

Green synthesis of enantiopure (S)‐1‐(benzofuran‐2‐yl)ethanol by whole‐cell biocatalyst

Chiral Bifunctional Ferrocenylphosphine‐Catalyzed Enantioselective Allylic Alkylation of Morita−Baylis−Hillman Carbonates with Pyrazolin‐5‐ones

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