Synthesis of enantiopure aliphatic acetylene alcohols and determination of their absolute configurations by 1H NMR anisotropy and/or X-ray crystallography

Satoshi Sekiguchi; Megumi Akagi; Junpei Naito; Yoko Yamamoto; Hiromi Taji; Shunsuke Kuwahara; Masataka Watanabe; Yoshiki Ozawa; Koshiro Toriumi; Nobuyuki Harada

doi:10.1002/ejoc.200800012

Synthesis of enantiopure aliphatic acetylene alcohols and determination of their absolute configurations by ¹H NMR anisotropy and/or X-ray crystallography

Satoshi Sekiguchi, Megumi Akagi, Junpei Naito, Yoko Yamamoto, Hiromi Taji, Shunsuke Kuwahara, Masataka Watanabe, Yoshiki Ozawa, Koshiro Toriumi, Nobuyuki Harada

Research output: Contribution to journal › Article › peer-review

16 Citations (Scopus)

Abstract

The MαNP acid method has been applied to racemic aliphatic acetylene alcohols in order to simultaneously prepare enantiopure alcohols and to determine their absolute configurations by ¹H NMR anisotropy. Racemic acetylene alcohols 6-8, 11, and 20 were esterified with MαNP acid (S)-(+)-1 to yield diastereomericMαNP esters which were efficiently separated by HPLC on silica gel with separation factors α in the range 1.60-1.93. The ¹H NMR anisotropy factors Δδ [= δ(2nd fr.) - δ(1st fr.)] were calculated from the data of the first- (22a-27a) and second-eluted MαNP esters (22b-27b). The absolute configurations of the first-eluted esters were determined from the distribution of Δδ values in the MαNP sector rule. In the case of MαNP ester 26b, the assigned absolute configuration was confirmed by X-ray crystallography. The solvolysis of MαNP esters yielded enantiopure acetylene alcohols 5-8 with established absolute configurations.

Original language	English
Pages (from-to)	2313-2324
Number of pages	12
Journal	European Journal of Organic Chemistry
Issue number	13
DOIs	https://doi.org/10.1002/ejoc.200800012
Publication status	Published - 2008 May

Keywords

Absolute configuration
Acetylene alcohols
Configuration determination
MαNP esters
NMR anisotropy
X-ray diffraction

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Organic Chemistry

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Sekiguchi, S., Akagi, M., Naito, J., Yamamoto, Y., Taji, H., Kuwahara, S., Watanabe, M., Ozawa, Y., Toriumi, K., & Harada, N. (2008). Synthesis of enantiopure aliphatic acetylene alcohols and determination of their absolute configurations by ¹H NMR anisotropy and/or X-ray crystallography. European Journal of Organic Chemistry, (13), 2313-2324. https://doi.org/10.1002/ejoc.200800012

Synthesis of enantiopure aliphatic acetylene alcohols and determination of their absolute configurations by ¹H NMR anisotropy and/or X-ray crystallography. / Sekiguchi, Satoshi; Akagi, Megumi; Naito, Junpei; Yamamoto, Yoko; Taji, Hiromi; Kuwahara, Shunsuke; Watanabe, Masataka; Ozawa, Yoshiki; Toriumi, Koshiro; Harada, Nobuyuki.

In: European Journal of Organic Chemistry, No. 13, 05.2008, p. 2313-2324.

Research output: Contribution to journal › Article › peer-review

Sekiguchi, S, Akagi, M, Naito, J, Yamamoto, Y, Taji, H, Kuwahara, S, Watanabe, M, Ozawa, Y, Toriumi, K & Harada, N 2008, 'Synthesis of enantiopure aliphatic acetylene alcohols and determination of their absolute configurations by ¹H NMR anisotropy and/or X-ray crystallography', European Journal of Organic Chemistry, no. 13, pp. 2313-2324. https://doi.org/10.1002/ejoc.200800012

Sekiguchi, Satoshi ; Akagi, Megumi ; Naito, Junpei ; Yamamoto, Yoko ; Taji, Hiromi ; Kuwahara, Shunsuke ; Watanabe, Masataka ; Ozawa, Yoshiki ; Toriumi, Koshiro ; Harada, Nobuyuki. / Synthesis of enantiopure aliphatic acetylene alcohols and determination of their absolute configurations by ¹H NMR anisotropy and/or X-ray crystallography. In: European Journal of Organic Chemistry. 2008 ; No. 13. pp. 2313-2324.

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abstract = "The MαNP acid method has been applied to racemic aliphatic acetylene alcohols in order to simultaneously prepare enantiopure alcohols and to determine their absolute configurations by 1H NMR anisotropy. Racemic acetylene alcohols 6-8, 11, and 20 were esterified with MαNP acid (S)-(+)-1 to yield diastereomericMαNP esters which were efficiently separated by HPLC on silica gel with separation factors α in the range 1.60-1.93. The 1H NMR anisotropy factors Δδ [= δ(2nd fr.) - δ(1st fr.)] were calculated from the data of the first- (22a-27a) and second-eluted MαNP esters (22b-27b). The absolute configurations of the first-eluted esters were determined from the distribution of Δδ values in the MαNP sector rule. In the case of MαNP ester 26b, the assigned absolute configuration was confirmed by X-ray crystallography. The solvolysis of MαNP esters yielded enantiopure acetylene alcohols 5-8 with established absolute configurations.",

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author = "Satoshi Sekiguchi and Megumi Akagi and Junpei Naito and Yoko Yamamoto and Hiromi Taji and Shunsuke Kuwahara and Masataka Watanabe and Yoshiki Ozawa and Koshiro Toriumi and Nobuyuki Harada",

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