A general method for the synthesis of enantiopure aliphatic chain alcohols with established absolute configurations. Part 2, via catalytic reduction of acetylene alcohol MαNP esters

Akagi, Megumi; Sekiguchi, Satoshi; Taji, Hiromi; Kasai, Yusuke; Kuwahara, Shunsuke; Watanabe, Masataka; Harada, Nobuyuki

doi:10.1016/j.tetasy.2014.10.005

Cited by 9 publications

(31 citation statements)

References 20 publications

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“…Of course, the (R) AC of alcohol (−)-39 was unambiguously determined by the chemical conversion. 77 It should be noted that the observed specific rotation value of alcohol (−)-39 was smaller than the standard deviation of measurement error, and hence the assignment of the negative sign is not reliable. However, at the moment, we have no method to specify the enantiomer of alcohol 39, and therefore, we used the observed negative sign here.…”

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

confidence: 94%

“…The hydrolysis of ester ( S ;19 S )‐(−)‐ 38a yielded enantiopure acetylene alcohol ( S )‐(−)‐ 37 , whose AC was unambiguously determined, as shown in Figure B. The MαNP acid method is also very useful for the synthesis of crypto‐chiral saturated long chain alcohols like 19‐octatriacontanol ( R )‐(−)‐ 39 , where a side chain is composed of ‐(CH 2 ) 18 CH 3 , while the other side chain is composed of ‐(CH 2 ) 17 CH 3 . Thus, the difference is only one CH 2 unit, and hence the optical rotation value would be extremely small.…”

Section: Relative Methods For Ac Determinationmentioning

confidence: 99%

“…The first‐eluted MαNP ester ( S ;19 S )‐(−)‐ 38a was hydrogenated to yield a saturated alcohol MαNP ester, which was successively hydrolyzed to afford a crypto‐chiral alcohol ( R )‐(−)‐ 39 in an enantiopure form. Of course, the ( R ) AC of alcohol (−)‐ 39 was unambiguously determined by the chemical conversion …”

Section: Relative Methods For Ac Determinationmentioning

confidence: 99%

“…Thus, the assignment of 19‐octatriacontanol ( R )‐(−)‐ 39 is logically supported. Anyway, it should be emphasized that the MαNP acid method is useful even for the synthesis of such a crypto‐chiral compound with established AC …”

Section: Relative Methods For Ac Determinationmentioning

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: The Internal Reference Methods Using 1 H Nmr Diamagnetic Anmentioning

confidence: 94%

Section: Relative Methods For Ac Determinationmentioning

confidence: 99%

Section: Relative Methods For Ac Determinationmentioning

confidence: 99%

Section: Relative Methods For Ac Determinationmentioning

confidence: 99%

See 2 more Smart Citations

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

Harada

2017

Chirality

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“…To prepare enantiopure compounds, we have developed the MaNP acid resolution method, [1][2][3][4][5][6][7][8][9][10][11][12] where (S)-(+)-2-methoxy-2-(1-naphthyl)propionic acid 1 (MaNP acid, Fig. 1) is reacted with a racemic secondary alcohol to yield diastereomeric esters, which are readily separable by HPLC on silica gel.…”

Section: Introductionmentioning

confidence: 99%

Application of the modified 2-methoxy-2-(1-naphthyl)propionic (MαNP) acid method to steroidal alcohols and the most efficient HPLC separation found in diastereomeric MαNP esters

Kasai

Harada

2015

Tetrahedron: Asymmetry

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2018

Differentiation of Chiral Compounds Using NMR Spectroscopy

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A general method for the synthesis of enantiopure aliphatic chain alcohols with established absolute configurations. Part 2, via catalytic reduction of acetylene alcohol MαNP esters

Cited by 9 publications

References 20 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”

Application of the modified 2-methoxy-2-(1-naphthyl)propionic (MαNP) acid method to steroidal alcohols and the most efficient HPLC separation found in diastereomeric MαNP esters

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