Chemoenzymatic Synthesis of α-Substituted Serines via Enantiodivergent Transformation

Sano, Shigeki; Nakao, Michiyasu; Takeyasu, Masanori; Yamamoto, Chiyo; Kitaike, Syuji; Yoshioka, Yasuko; Nagao, Yoshimitsu

doi:10.2174/1874095200903010022

TOOCJ

2009

DOI: 10.2174/1874095200903010022

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Chemoenzymatic Synthesis of α-Substituted Serines via Enantiodivergent Transformation

Shigeki Sano¹,

Michiyasu Nakao²,

Masanori Takeyasu³

et al.

Abstract: A series of (R)-N-Cbz-2-alkyl-2-amino-3-hydroxypropyl acetates was prepared by enzymatic acetylation of NCbz-2-alkyl-2-aminopropane-1,3-diols with immobilized lipoprotein lipase from Pseudomonas sp. in up to 98% enantiomeric excess (ee). Enantiodivergent oxidation of (R)-N-Cbz-2-alkyl-2-amino-3-hydroxypropyl acetates readily furnished (R)-and (S)--substituted serines ( -benzylserines and -methylserines). Enzymatic hydrolysis of diethyl N-Cbz-2-amino-2-methylmalonate catalyzed by porcine liver esterase afforded… Show more

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Cited by 4 publications

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First Stereoselective Synthesis of Diethyl cis- and trans-(4-Hydroxy-1,2,3,4-tetrahydroquinolin-2-yl)phosphonates and Ethyl Phenylphosphinates from Quinolin-4(1H)-one

Ordóñez,

Argüello-Velasco,

Miranda-Blancas

et al. 2023

Synthesis

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We report here a practical method for the first stereoselective synthesis of novel diethyl cis- and trans-(4-hydroxy-1,2,3,4-tetrahydro-quinolin-2-yl)phosphonates, as well as the ethyl cis- and trans-(4-hydroxy-1,2,3,4-tetrahydroquinolin-2-yl)phenylphosphinates. The main feature of this method involves the regioselective 1,4-phosponylation to N-Cbz quinolin-4(1H)-one using diethyl phosphite or ethyl phenylphosphinate followed by the high diastereoselective reduction, to give the cis stereoisomers as favored products, which through the Mitsunobu reaction were converted into trans stereoisomers. Cleavage of N-Cbz bond under hydrogenolysis, gave the target heterocyclic α-aminophosphonates and α-aminophosphinates.

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First Stereoselective Synthesis of Diethyl cis- and trans-(4-Hydroxy-1,2,3,4-tetrahydroquinolin-2-yl)phosphonates and Ethyl Phenylphosphinates from Quinolin-4(1H)-one

Ordóñez,

Argüello-Velasco,

Miranda-Blancas

et al. 2023

Synthesis

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Development of Novel Functional Molecules Based on the Molecular Structure Characteristics of Diketopiperazines

Nakao

2017

YAKUGAKU ZASSHI

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This article focuses on our investigation of the molecular structure characteristics of diketopiperazines (DKPs), and application of theseˆndings to the development of novel functional molecules. DKPs bearing a benzyl moiety are known to adopt a folded conformation, in which the benzyl moiety is folded over the DKP ring. In order to investigate the driving force behind the folded conformation, we synthesized DKPs bearing a benzyl moiety with diŠerent para-substituents, and demonstrated that the folded conformation likely arose from intramolecular CH/p interactions, based on the electronic eŠects of para-substituents on the benzyl group in 1 H NMR spectroscopy. On the other hand, N4-methylation of DKPs bearing a benzyl moiety was found to change their folded conformation to an extended conformation, based on single crystal X-ray crystallography and 1 H NMR spectroscopy analysis. Next, we attempted to synthesize both hydroxamate-type siderophores containing the DKP ring: rhodotorulic acid and erythrochelin. Facile synthesis of rhodotorulic acid and its N,N′ -dimethylated derivative was achieved by microwave-assisted cyclization of the corresponding dipeptide precursors. Interestingly, N,N′ -dimethylated rhodotorulic acid was found to be more soluble in various organic solvents than rhodotorulic acid. Moreover, erythrochelin was synthesized for theˆrst time, and its metal-chelating ability with not only Fe(III) but also Mg(II) was conˆrmed based on electrospray ionization mass spectrometry (ESI-MS) analysis. Finally, we synthesized DKPs bearing a primary amino group, and found that they could catalyze the asymmetric aldol reaction between hydroxyacetone and p-nitrobenzaldehyde.

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Catalytic Asymmetric Ring-Opening of σ-Symmetric Cyclic Carbonates with Chiral Amino Sulfonamide Catalysts

Nakao¹,

Shozui²,

Inoue³

et al. 2021

HETEROCYCLES

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Enantioselective ring-opening of σ-symmetric six-membered cyclic carbonates with benzyl alcohol catalyzed by 20 mol% of chiral amino sulfonamide catalysts afforded chiral acyclic carbonates in up to 79% ee.Catalytic asymmetric desymmetrization is a general and convenient strategy for asymmetric synthesis. [1][2][3][4][5][6][7] We have developed several enzymatic or nonenzymatic catalytic asymmetric desymmetrizations of σ-symmetric compounds, such as 1,3-diesters, 8-10 cyclic anhydrides, 11-13 1,3-diols, 10,14-17 and cyclic carbonates. 18 In the desymmetrization of σ-symmetric six-membered cyclic carbonate 1a, a catalytic amount of BINOL-based phosphoric acid 2 was used as a chiral Brønsted acid catalyst. As a result, asymmetric ring-opening of 1a with 2 afforded the acyclic carbonate (S)-3a in 94% yield with 81% ee as shown in Scheme 1. 19

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Chemoenzymatic Synthesis of α-Substituted Serines via Enantiodivergent Transformation

Cited by 4 publications

References 4 publications

First Stereoselective Synthesis of Diethyl cis- and trans-(4-Hydroxy-1,2,3,4-tetrahydroquinolin-2-yl)phosphonates and Ethyl Phenylphosphinates from Quinolin-4(1H)-one

First Stereoselective Synthesis of Diethyl cis- and trans-(4-Hydroxy-1,2,3,4-tetrahydroquinolin-2-yl)phosphonates and Ethyl Phenylphosphinates from Quinolin-4(1H)-one

Development of Novel Functional Molecules Based on the Molecular Structure Characteristics of Diketopiperazines

Catalytic Asymmetric Ring-Opening of σ-Symmetric Cyclic Carbonates with Chiral Amino Sulfonamide Catalysts

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