Synthesis of optically active heterocyclic compounds via deracemization of 1,2-diol monotosylate derivatives bearing a long aliphatic chain by a combination of enzymatic hydrolysis with Mitsunobu inversion

Matsumoto, Kazutsugu; Usuda, Kazumasa; Okabe, Hirokazu; Hashimoto, Manabu; Shimada, Yasutaka

doi:10.1016/j.tetasy.2012.11.023

Cited by 20 publications

(14 citation statements)

References 41 publications

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“…( R )‐2‐(4‐(Benzyloxy)butyl)oxirane (14): Prepared from 13 according to the representative procedure, 14 was isolated as a colorless oil, 65 % yield (344 mg); 1 H NMR (200 MHz, CDCl 3 ) δ 7.34–7.25 (5H, m, ArH), 4.51 (2H, s, ArCH 2 ), 3.49 (2H, t, J = 6.2 Hz, OCH 2 ), 2.93–2.89 (1H, m, OCH), 2.77–2.72 (1H, m, OCH), 2.46 (1H, dd, J = 4.9, 2.0 Hz, OCH), 1.76–1.48 (6H, m, 6 × C H H); 13 C NMR (50 MHz, CDCl 3 ) δ 138.4, 128.2, 127.5, 127.4, 72.8, 70.0, 52.2, 47.0, 32.1, 29.4, 22.6; [ α ] D 20 = +4.5 ( c = 1.0, CHCl 3 ). For ( S )‐epoxide [ α ] D 26 = –5.3 ( c = 1.4, CHCl 3 ) and [ α ] D 20 = –5.1 ( c = 2.3, CHCl 3 );, HRMS (ESI + ): m/z calcd.…”

Section: Methodsmentioning

confidence: 99%

Asymmetric Synthesis of Saturated Hydroxy Fatty Acids and Fatty Acid Esters of Hydroxy Fatty Acids

et al. 2019

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The recent discovery of a novel class of endogenous lipids, named Fatty Acid esters of Hydroxy Fatty Acids (FAHFAs), that present antidiabetic and anti‐inflammatory activities, has attracted the interest on hydroxy fatty acids (HFAs) and their derivatives. We present herein the development of a convenient and general methodology for the asymmetric synthesis of HFAs and FAHFAs. The enantioselective organocatalytic synthesis of asymmetric terminal epoxides starting from monoprotected α,ω‐diols and their subsequent ring opening by a Grignard reagent are the key‐steps for our methodology, allowing the introduction of the hydroxy group at different positions of the long chain by proper selection of the starting diol and the Grignard reagent. MacMillan's third generation imidazolidinone organocatalyst has been employed for the epoxide formation, ensuring products in high enantiomeric purity. Furthermore, an approach for the synthesis of deuterated HFAs and FAHFAs was developed, leading to deuterated derivatives, which can be useful in biological studies and in mass spectrometry studies as internal standards.

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Section: Methodsmentioning

confidence: 99%

Asymmetric Synthesis of Saturated Hydroxy Fatty Acids and Fatty Acid Esters of Hydroxy Fatty Acids

et al. 2019

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“…The sequential deracemisation combining the two steps led to the final 2‐acetoxy‐1‐tosylated diols with excellent optical purities (93–98% ee ) and high yields (73–91%), depending on the substrate structure. Such a protocol was successfully applied for the preparation of valuable heterocyclic compounds such as alkaloids and insect pheromones as well as fragrance compounds …”

Section: Enzymatic Deracemisation Proceduresmentioning

confidence: 99%

Deracemisation Processes Employing Organocatalysis and Enzyme Catalysis

et al. 2020

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Deracemisation methods have demonstrated their importance in the preparation of chiral compounds in the last few years. In order to resolve a racemic mixture in a dynamic sense, one enantiomer of the starting material can be converted to the other through a deracemisation procedure, that can be achieved by different mechanisms based on stereoinversion or enantioconvergence, often involving two‐opposite half reactions, with at least one of the reactions being enantioselective enough to finally obtain an enantioenriched chiral compound. The focus of this comprehensive review is on the application of deracemisation procedures in the present century in order to obtain optically active valuable compounds when employing non‐metallic catalysts. Thus, the review will mainly focus on the use of different enzymatic preparations (purified enzymes, cell‐free extracts or whole cell systems) and organocatalysts for the deracemisation of racemic mixtures.

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“…114 An interesting chemoenzymatic enantioconvergent method was reported by Matsumoto and coworkers (Scheme 29). 115,116 Racemic acetate esters were first Scheme 26 Deracemisation of secondary alcohols (using a nonstereoselective ADH) coupled to reductive amination with reductive aminases (e.g., from Aspergillus, AspRedAm). ADHs used in this study were W110A TeSADH and the ADH from Sphingobium yanoikuyae (SyADH).…”

Section: Enantioconvergent Deracemisation Reactionsmentioning

confidence: 99%

Synthesis of enantiomerically pure alcohols and amines via biocatalytic deracemisation methods

Musa

Hollmann

Mutti

2019

Catal. Sci. Technol.

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Synthesis of optically active heterocyclic compounds via deracemization of 1,2-diol monotosylate derivatives bearing a long aliphatic chain by a combination of enzymatic hydrolysis with Mitsunobu inversion

Cited by 20 publications

References 41 publications

Asymmetric Synthesis of Saturated Hydroxy Fatty Acids and Fatty Acid Esters of Hydroxy Fatty Acids

Asymmetric Synthesis of Saturated Hydroxy Fatty Acids and Fatty Acid Esters of Hydroxy Fatty Acids

Deracemisation Processes Employing Organocatalysis and Enzyme Catalysis

Synthesis of enantiomerically pure alcohols and amines via biocatalytic deracemisation methods

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