کد مقاله کد نشریه سال انتشار مقاله انگلیسی نسخه تمام متن
1343792 980036 2014 10 صفحه PDF دانلود رایگان
عنوان انگلیسی مقاله ISI
A general method for the synthesis of enantiopure aliphatic chain alcohols with established absolute configurations. Part 1. Application of the MαNP acid method to acetylene alcohols
موضوعات مرتبط
مهندسی و علوم پایه شیمی شیمی معدنی
پیش نمایش صفحه اول مقاله
A general method for the synthesis of enantiopure aliphatic chain alcohols with established absolute configurations. Part 1. Application of the MαNP acid method to acetylene alcohols
چکیده انگلیسی

A method using (S)-(+)-2-methoxy-2-(1-naphthyl)propionic acid 1 (MαNP acid) has been applied to acetylene alcohols 4–14 to determine their absolute configurations by 1H NMR anisotropy and/or X-ray crystallography. Diastereomeric MαNP esters prepared from racemic acetylene alcohols and (S)-(+)-MαNP acid 1 were easily separable by HPLC on silica gel. From the 1H NMR anisotropy Δδ data of separated diastereomeric MαNP esters {Δδ = δ (R,X) − δ(S,X) = δ(2nd fr.) − δ(1st fr.)}, the absolute configurations of the first eluted esters were determined. This MαNP acid method has been successfully applied to various acetylene alcohols 4–12 and 14. In the case of MαNP esters 21b, 24a, and 26a, their absolute configurations were unambiguously determined by X-ray crystallography, which confirmed the absolute configuration assignments performed by 1H NMR anisotropy. These acetylene alcohol MαNP esters can serve as key intermediates for the synthesis of enantiopure aliphatic chain alcohols with established absolute configurations as described in Part 2 of this series.

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(S)-3-Butyn-2-yl-(S)-2-methoxy-2-(1-naphthyl)propionateC18H18O3Ee = 100%[α]D23 = −55.2 (c 2.26, CHCl3)Source of chirality: enantioresolutionAbsolute conf iguration: (S,S) determined by 1H NMR.

(R)-3-Butyn-2-yl (S)-2-methoxy-2-(1-naphthyl)propionateC18H18O3Ee = 100%[α]D23 = +0.5 (c 2.19, CHCl3)Source of chirality: enantioresolutionAbsolute configuration: (R,S) determined by 1H NMR and X-ray

(S)-1-Pentyn-3-yl (S)-2-methoxy-2-(1-naphthyl)propionateC19H20O3Ee = 100%[α]D21 = −57.5 (c 2.18, CHCl3)Source of chirality: enantioresolutionAbsolute configuration: (S,S) determined by 1H NMR

(R)-1-Pentyn-3-yl (S)-2-methoxy-2-(1-naphthyl)propionateC19H20O3Ee = 100%[α]D21 = −0.51 (c 1.82, CHCl3)Source of chirality: enantioresolutionAbsolute configuration: (R,S) determined by 1H NMR

(S)-1-Hexyn-3-yl (S)-2-methoxy-2-(1-naphthyl)propionateC20H22O3Ee = 100%[α]D23 = −61.6 (c 1.57, CHCl3)Source of chirality: enantioresolutionAbsolute configuration: (S,S) determined by 1H NMR

(R)-1-Hexyn-3-yl (S)-2-methoxy-2-(1-naphthyl)propionateC20H22O3Ee = 100%[α]D23 = +2.8 (c 1.60, CHCl3)Source of chirality: enantioresolutionAbsolute configuration: (R,S) determined by 1H NMR

(S)-5-Methyl-1-hexyn-3-yl (S)-2-methoxy-2-(1-naphthyl)propionateC21H24O3Ee = 100%[α]D27 = −62.4 (c 1.73, CHCl3)Source of chirality: enantioresolutionAbsolute configuration: (S,S) determined by 1H NMR and X-ray

(R)-5-Methyl-1-hexyn-3-yl (S)-2-methoxy-2-(1-naphthyl)propionateC21H24O3Ee = 100%[α]D27 = +12.5 (c 2.26, CHCl3)Source of chirality: enantioresolutionAbsolute configuration: (R,S) determined by 1H NMR

(S)-1-Heptyn-3-yl (S)-2-methoxy-2-(1-naphthyl)propionateC21H24O3Ee = 100%[α]D22 = −56.8 (c 1.33, CHCl3)Source of chirality: enantioresolutionAbsolute configuration: (S,S) determined by 1H NMR

(R)-1-Heptyn-3-yl (S)-2-methoxy-2-(1-naphthyl)propionateC21H24O3Ee = 100%[α]D23 = −5.0 (c 1.28, CHCl3)Source of chirality: enantioresolutionAbsolute configuration: (R,S) determined by 1H NMR

(R)-1-Phenyl-2-propyn-1-yl (S)-2-methoxy-2-(1-naphthyl)propionateC23H20O3Ee = 100%[α]D25 = −41.1 (c 2.67, CHCl3)Source of chirality: enantioresolutionAbsolute configuration: (R,S) determined by 1H NMR and X-ray

(S)-1-Phenyl-2-propyn-1-yl (S)-2-methoxy-2-(1-naphthyl)propionateC23H20O3Ee = 100%[α]D23 = −51.3 (c 2.48, CHCl3)Source of chirality: enantioresolutionAbsolute configuration: (S,S) determined by 1H NMR

(S)-5-Octyn-4-yl (S)-2-methoxy-2-(1-naphthyl)propionateC22H26O3Ee = 100%[α]D22 = −62.0 (c 1.13, CHCl3)Source of chirality: enantioresolutionAbsolute configuration: (S,S) determined by 1H NMR

(R)-5-Octyn-4-yl (S)-2-methoxy-2-(1-naphthyl)propionateC22H26O3Ee = 100%[α]D23 = −3.7 (c 1.06, CHCl3)Source of chirality: enantioresolutionAbsolute configuration: (R,S) determined by 1H NMR

(S)-8-Nonadecyn-10-yl (S)-2-methoxy-2-(1-naphthyl)propionateC33H48O3Ee = 100%[α]D27 = −39.8 (c 1.60, CHCl3)Source of chirality: enantioresolutionAbsolute configuration: (S,S) determined by 1H NMR

(R)-8-Nonadecyn-10-yl (S)-2-methoxy-2-(1-naphthyl)propionateC33H48O3Ee = 100%[α]D27 = −5.2 (c 1.44, CHCl3)Source of chirality: enantioresolutionAbsolute configuration: (R,S) determined by 1H NMR

(S)-1-Nonadecen-11-yn-10-yl (S)-2-methoxy-2-(1-naphthyl)propionateC33H46O3Ee = 100%[α]D24 = −40.6 (c 1.32, CHCl3)Source of chirality: enantioresolutionAbsolute configuration: (S,S) determined by 1H NMR

(R)-1-Nonadecen-11-yn-10-yl (S)-2-methoxy-2-(1-naphthyl)propionateC33H46O3Ee = 100%[α]D25 = −5.3 (c 1.11, CHCl3)Source of chirality: enantioresolutionAbsolute configuration: (R,S) determined by 1H NMR

(S)-6-Methyl-1-heptyn-4-yl (S)-2-methoxy-2-(1-naphthyl)propionateC22H26O3Ee = 100%[α]D26 = −43.5 (c 1.03, CHCl3)Source of chirality: enantioresolutionAbsolute configuration: (S,S) determined by 1H NMR

(R)-6-Methyl-1-heptyn-4-yl (S)-2-methoxy-2-(1-naphthyl)propionateC22H26O3Ee = 100%[α]D26 = +16.2 (c 2.41, CHCl3)Source of chirality: enantioresolutionAbsolute configuration: (R,S) determined by 1H NMR

ناشر
Database: Elsevier - ScienceDirect (ساینس دایرکت)
Journal: Tetrahedron: Asymmetry - Volume 25, Issue 22, 30 November 2014, Pages 1456–1465
نویسندگان
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