An Effective and Environmentally Friendly Synthesis of 1,3-Keto-alcohols

Yıldız, Tülay; Can, Hacer; Yusufoğlu, Ayşe

doi:10.1080/00304948.2019.1693239

Cited by 4 publications

(6 citation statements)

References 31 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Gratifyingly, we found that the reaction of 1a with 2a was accomplished with an improved yield (92%) and selectivity ( anti / syn 91:9; 85% ee ) in DMSO–H 2 O (8:2) (Table , entry 10). Especially in asymmetric aldol reactions, it is preferred together with DMSO and some water, and it has been used in many previous studies. − Moreover, the reports prepared by the U.S. Environmental Protection Agency have mentioned that DMSO is a nontoxic solvent that does not harm human health…”

Section: Resultsmentioning

confidence: 99%

“…Especially in asymmetric aldol reactions, it is preferred together with DMSO and some water, and it has been used in many previous studies. 46 − 49 Moreover, the reports prepared by the U.S. Environmental Protection Agency have mentioned that DMSO is a nontoxic solvent that does not harm human health. 50…”

Section: Resultsmentioning

confidence: 99%

“…Reactions were monitored by thinlayer chromatography (TLC) using silica gel plates, and the products were purified by flash column chromatography on silica gel (230−400 mesh). NMR spectroscopy was conducted at 500 MHz for 1 H and 125 MHz for 13 ■ GENERAL PROCEDURE FOR THE SYNTHESIS OF THE RACEMIC 1,3-KETO ALCOHOLS (PROCEDURE I) 49 The synthesis of racemic 1,3-keto alcohols was carried out by applying the new modified method previously developed by us, by aldol condensation in the presence of a suitable ketone and aldehyde. 49 ■ GENERAL PROCEDURE FOR THE SYNTHESIS OF…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

See 2 more Smart Citations

New Strategy for the Synthesis of Some Valuable Chiral 1,3-Diols with High Enantiomeric Purity: New Organocatalyst, Asymmetric Aldol Reaction, and Reduction

Yıldız,

Hasdemir,

Yaşa

et al. 2024

ACS Omega

Self Cite

View full text Add to dashboard Cite

Chiral 1,3-diols are highly valuable molecules used in industries such as pharmaceuticals, cosmetics, and agriculture. Therefore, in this study, a new strategy was developed to synthesize enantiomerically pure (>99% ee) 1,3-diols. New chiral 1,3-diols (5a−5q) with high enantiomeric purity were synthesized from aldol products chiral 1,3-keto alcohols (4a−4q), which are aldol products with different structures. Chiral 1,3-keto alcohols (4a−4q) were synthesized by a new asymmetric aldol method in the first step. This method was developed using a new proline-derived organocatalyst (3g) and Cu(OTf) 2 as an additive in DMSO−H 2 O for the first time. Almost >99% ee was obtained using our developed aldol procedure. In the second step, original chiral diols (5a−5q) of high enantiomeric purity were obtained by asymmetric reduction of chiral keto alcohols with chiral oxazaborolidine reagents. In this way, a two-step asymmetric reaction was developed for chiral 1,3-diol enantiomers with high enantiomeric purity. The structures of all the original chiral compounds obtained were elucidated by infrared and nuclear magnetic resonance spectroscopy, mass spectrometry, and elemental analysis methods. Their enantiomeric excesses were determined by the chiral high-performance liquid chromatography method. Both keto alcohols and their corresponding chiral diols synthesized can be used as chiral starting materials and chiral source materials or intermediates in the synthesis of many biologically active molecules, or they can be used as chiral ligands in asymmetric synthesis, serving as organocatalysts.

show abstract

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: ■ Experimental Sectionmentioning

confidence: 99%

See 1 more Smart Citation

New Strategy for the Synthesis of Some Valuable Chiral 1,3-Diols with High Enantiomeric Purity: New Organocatalyst, Asymmetric Aldol Reaction, and Reduction

Yıldız,

Hasdemir,

Yaşa

et al. 2024

ACS Omega

Self Cite

View full text Add to dashboard Cite

show abstract

“…Initially, the aldol product 1 a was prepared using a suitable aldehyde (benzaldehyde) and ketone (acetone) for a classic aldol reaction using K 2 CO 3 as a base. [21] After that, the racemic aldol product 1 a was separated into chiral enantiomers using two biochemical resolution methods. For the EKR method, six commercially available lipase enzymes and two liver acetone powders, which provide low-cost crude lipase sources, were used as crude biocatalysts.…”

Section: Resultsmentioning

confidence: 99%

“…Initially, the aldol product 1 a was prepared using a suitable aldehyde (benzaldehyde) and ketone (acetone) for a classic aldol reaction using K 2 CO 3 as a base . After that, the racemic aldol product 1 a was separated into chiral enantiomers using two biochemical resolution methods.…”

Section: Resultsmentioning

confidence: 99%

Synthesis of Chiral 1,3‐keto‐acetates through Enzymatic Kinetic Resolution with Amano Lipase fromPseudomonas fluorescens

2020

Self Cite

View full text Add to dashboard Cite

This study provides an enzymatic kinetic resolution (EKR) method for the biocatalytic enantioselective synthesis of chiral β-keto acetates. For the first time, the attitude of several lipase enzymes has been examined under different conditions for the EKR of the racemic 1,3-keto alcohols. We found that the Amano lipase from Pseudomonas fluorescens (AL-PF) lipase showed the best results for the resolution of the racemic 1,3-keto alcohols. We developed a highly effective EKR method by changing the enzyme, temperature, solvent, and enzyme amount in order to synthesize the chiral 1,3-keto esters, which are useful intermediates in organic synthesis. This study presents an efficient method for the synthesis of 1,3-keto acetates with a good yield and high enantioselectivity with the R configuration.

show abstract

Synthesis and Characterization of New Bulky α‐Hydroxy Ketones by N‐Heterocyclic Carbene‐Catalyzed Intramolecular Benzoin Condensation

Hasdemir,

Alhallak,

Yıldız

2024

ChemistrySelect

View full text Add to dashboard Cite

Intramolecular benzoin condensation, which is a powerful and useful method for the formation of carbon−carbon bonds from aldehydes, is also an advantageous method for the preparation of a wide variety of α‐hydroxy ketones. The α‐Hydroxy carbonyl groups are an important structure for natural products, industrial, and pharmaceutical materials. In this study, it was aimed to synthesize new bulky α‐hydroxy ketones that can be used both as pharmaceutical materials and can lead to the synthesis of new organocatalysts. An effective method was applied for the synthesis of bulky hydroxy ketones 2 a–l using intramolecular benzoin condensation catalyzed by N‐heterocyclic carbene (I) from 4‐arenoxybenzaldehyde 1 a–f or 4‐thioetherbenzaldehyde 1 g–l derivatives and 12 new bulky α‐hydroxy ketone compounds 2 a–l were synthesized in 70–87 % isolated yield. The synthesized compounds were characterized by spectroscopic and chromatographic methods such as FT‐IR, NMR, LC–MS, and CHN analysis. Additionally, compound 2 h selected as a model substrate was converted into 1,2 diol 3 h, 1,2‐diketone 4 h, and 1,2‐keto acetate 5 h derivatives, and structural analyses were performed. Moreover, chiral hydroxy ketone 2 h was obtained with 100 % ee due to the enzymatic hydrolysis reaction catalyzed by Lipase from Candida rugosa (CRL).

show abstract

An Effective and Environmentally Friendly Synthesis of 1,3-Keto-alcohols

Cited by 4 publications

References 31 publications

New Strategy for the Synthesis of Some Valuable Chiral 1,3-Diols with High Enantiomeric Purity: New Organocatalyst, Asymmetric Aldol Reaction, and Reduction

New Strategy for the Synthesis of Some Valuable Chiral 1,3-Diols with High Enantiomeric Purity: New Organocatalyst, Asymmetric Aldol Reaction, and Reduction

Synthesis of Chiral 1,3‐keto‐acetates through Enzymatic Kinetic Resolution with Amano Lipase fromPseudomonas fluorescens

Synthesis and Characterization of New Bulky α‐Hydroxy Ketones by N‐Heterocyclic Carbene‐Catalyzed Intramolecular Benzoin Condensation

Contact Info

Product

Resources

About