HPLC Separation of Diastereomers: Chiral  Molecular Tools Useful for the Preparation  of Enantiopure Compounds and Simultaneous Determination of Their Absolute Configurations

Harada, Nobuyuki

doi:10.3390/molecules21101328

Cited by 18 publications

(15 citation statements)

References 52 publications

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“…As one of these methods, N. Harada and coworkers developed the MαNP acid method, which has been successfully applied to many chiral secondary alcohols to determine their ACs (Figures and 24) . MαNP acid, 2‐methoxy‐2‐(1‐naphthyl)propionic acid ( S )‐(+)‐ 34 , is useful also as a chiral resolving reagent of alcohols.…”

Section: Relative Methods For Ac Determinationmentioning

confidence: 99%

“…two times larger than those of MPA esters The most important advantage of MαNP esters is that their diastereomeric esters formed from racemic alcohol and enantiopure MαNP acid are easily and largely separable by HPLC on silica gel: separation factor α ranges from 1.15 to 1.93; average α = 1.58 . Therefore, the M α NP acid method enables one to enantioresolve racemic alcohols and to determine their ACs simultaneously.…”

Section: Relative Methods For Ac Determinationmentioning

confidence: 99%

“…73 As one of these methods, N. Harada and coworkers developed the MαNP acid method, which has been successfully applied to many chiral secondary alcohols to determine their ACs (Figures 23 and 24). [52][53][54][55][56]74,75 MαNP acid, 2-methoxy-2-(1-naphthyl)propionic acid (S)-(+)-34, is useful also as a chiral resolving reagent of alcohols. Namely, as shown in Figure 24A, racemic alcohol (±)-35 is esterified with MαNP acid (S)-(+)-34 yielding diastereomeric esters, which are easily separable by HPLC on silica gel.…”

Section: The Internal Reference Methods Using 1 H Nmr Diamagnetic Anmentioning

confidence: 99%

“…For many other application examples of the MαNP acid method, see Refs. [52][53][54][55][56][74][75][76][77]80, and references cited therein.…”

Section: The Internal Reference Methods Using 1 H Nmr Diamagnetic Anmentioning

confidence: 99%

“…Internal Reference of AC [51][52][53][54][55][56] This is the most reliable and simple method for AC determination, where X-ray crystallography of a compound containing an internal reference with known AC is carried out. In this case, it is not necessary that the crystal has to contain a heavy atom.…”

Section: X-ray Crystallography Using Anmentioning

confidence: 99%

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Chiral Molecular Science: How were the absolute configurations of chiral molecules determined? “Experimental results and theories”

Harada

2017

Chirality

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Molecular chirality is a key concept in chemistry, bioscience, and molecular technology, like the invention of a light-powered chiral molecular motor explained in this review. Thus, the primary research subject is how to determine the absolute configuration (AC) of chiral compounds. This review article focuses on the principle, theory, and practice of the nonempirical methods for determining ACs of chiral compounds, i.e., the Bijvoet method in X-ray crystallography and the circular dichroism (CD) exciton chirality method, together with the historical aspects of AC determination. The theoretical equations of X-ray crystallography and exciton CD spectroscopy are explained in detail, and these equations are useful for readers to understand the principle and mechanism of these methods. This review also focuses on the relative methods, where the internal reference with known AC is used and the relative configuration is determined by X-ray crystallography and/or H nuclear magnetic resonance (NMR) diamagnetic anisotropy method. In these cases, CSDP acid and MαNP acid are useful for the chiral resolution of racemic alcohols, where their diastereomeric esters are easily separable by high-performance liquid chromatography (HPLC) on silica gel. Thus, these methods are useful for the preparation of enantiopure compounds and simultaneous determination of their ACs. In this review article, the above methods are explained mainly based on the author's own research results.

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Section: Relative Methods For Ac Determinationmentioning

confidence: 99%

Section: Relative Methods For Ac Determinationmentioning

confidence: 99%

Section: The Internal Reference Methods Using 1 H Nmr Diamagnetic Anmentioning

confidence: 99%

“…For many other application examples of the MαNP acid method, see Refs. [52][53][54][55][56][74][75][76][77]80, and references cited therein.…”

Section: The Internal Reference Methods Using 1 H Nmr Diamagnetic Anmentioning

confidence: 99%

Section: X-ray Crystallography Using Anmentioning

confidence: 99%

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Chiral Molecular Science: How were the absolute configurations of chiral molecules determined? “Experimental results and theories”

Harada

2017

Chirality

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Biochemistry‐Guided Prediction of the Absolute Configuration of Fungal Reduced Polyketides

et al. 2021

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Highly reducing polyketide synthases (HR‐PKSs) produce structurally diverse polyketides (PKs). The PK diversity is constructed by a variety of factors, including the β‐keto processing, chain length, methylation pattern, and relative and absolute configurations of the substituents. We examined the stereochemical course of the PK processing for the synthesis of polyhydroxy PKs such as phialotides, phomenoic acid, and ACR‐toxin. Heterologous expression of a HR‐PKS gene, a trans‐acting enoylreductase gene, and a truncated non‐ribosomal peptide synthetase gene resulted in the formation of a linear PK with multiple stereogenic centers. The absolute configurations of the stereogenic centers were determined by chemical degradation followed by comparison of the degradation products with synthetic standards. A stereochemical rule was proposed to explain the absolute configurations of other reduced PKs and highlights an error in the absolute configurations of a reported structure. The present work demonstrates that focused functional analysis of functionally related HR‐PKSs leads to a better understanding of the stereochemical course.

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One‐Handed Helical Polyacetylenes Bearing Axially‐Chiral 2‐Arylpyridyl‐N‐Oxide Units for Efficient Chromatographic Enantioseparation of Chiral Aromatic and Aliphatic Alcohols

et al. 2023

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A series of poly(biarylylacetylene)s (PBAs) bearing axially‐chiral (S)‐and (R)‐pyridyl‐N‐oxide residues with a methoxy, propoxy, or acetyloxy substituent at the 3‐position of the biaryl units was synthesized. All the PBAs formed a preferred‐handed helix, while the helical sense preference was varied depending on the substituents despite the same twist‐sense of the biaryl units. Among them, the propoxy‐bound helical PBA showed an exceptionally high chiral recognition ability as a chiral stationary phase (CSP) for high‐performance liquid chromatography (HPLC) and efficiently resolved not only various chiral aromatic alcohols, but also a variety of chiral aliphatic alcohols; the latter still remains difficult to resolve by commercially‐available CSPs in HPLC. Such practically‐useful both handed helical PBA‐based CSPs can be produced from the racemic PBA composed of fully racemic monomer units through deracemization of the biaryl units with a chiral alcohol.

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HPLC Separation of Diastereomers: Chiral Molecular Tools Useful for the Preparation of Enantiopure Compounds and Simultaneous Determination of Their Absolute Configurations

Cited by 18 publications

References 52 publications

Chiral Molecular Science: How were the absolute configurations of chiral molecules determined? “Experimental results and theories”

Chiral Molecular Science: How were the absolute configurations of chiral molecules determined? “Experimental results and theories”

Biochemistry‐Guided Prediction of the Absolute Configuration of Fungal Reduced Polyketides

One‐Handed Helical Polyacetylenes Bearing Axially‐Chiral 2‐Arylpyridyl‐N‐Oxide Units for Efficient Chromatographic Enantioseparation of Chiral Aromatic and Aliphatic Alcohols

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