The novel macrocyclic compounds as chiral solvating agents for determination of enantiomeric excess of carboxylic acids

The novel macrocyclic compounds 1–8 and acyclic compound 9 were designed and synthesized. 1H NMR studies demonstrated that 1 and 2 were the best chiral solvating agents, and are effective for the determination of the enantiomeric excess of a wide range of α-chiral carboxylic acids. Large non-equivalent chemical shifts (up to 411.2 Hz) can be achieved in the presence of 1 and 2. Quantitative analyses of a series of mandelic acids with different enantiomeric purities demonstrate that 1 and 2 are excellent chiral solvating agents for carboxylic acids.

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(12S,18S)-N12,N18-Bis[(1S)-1-phenylethyl]-{2H,8H,12H,18H-(3,7),(13,17)-dimetheno-dinaphtho[2,1-j:1′,2′-s][1,9] dioxacycloeicosin-12,18-diamine}C52H46N2O2[α]D20=+19.6 (c 0.23, THF)Source of chirality: (S)-α-phenylethylamineAbsolute configuration: (S,S,S,S)

(12S,18S)-N12,N18-Dimethyl-N12,N18-bis[(1S)-1-phenylethyl]-{2H,8H,12H,18H-13,17-metheno-3,7-nitrilo-dinaphtho[2,1-j:1′,2′-s][1,9]dioxacycloeicosin-12,18-diamine}C53H49N3O2[α]D20=+349.0 (c 0.67, THF)Source of chirality: (S)-α-phenylethylamineAbsolute configuration: (S,S,S,S)

(9S,15S)-N9,N15-Bis[(1S)-1-phenylethyl]-{2H,5H,9H,15H-10,14-metheno-benzo[c]-dinaphtho[2,1-g: 1′,2′-p][1,5]dioxacycloheptadecin-9,15-diamine}C52H46N2O2[α]D20=-2.1 (c 0.63, THF)Source of chirality: (S)-α-phenylethylamineAbsolute configuration: (S,S,S,S)

(11S,17S)-N11,N17-Bis[(1S)-1-phenylethyl]-{2H,7H,11H,17H-12,16-metheno-dibenzo[c:e]-dinaphtho[2,1-i:1′,2′-r] [1,8]dioxacyclonondecin-11,17-diamine}C58H50N2O2[α]D20=-62.4 (c 0.90, THF)Source of chirality: (S)-α-phenylethylamineAbsolute configuration: (S,S,S,S)

(12S,17S)-N12,N17-Bis[(1S)-1-phenylethyl]-{2H,8H,12H,17H-3,7-nitrilo-13,16-etheno-dinaphtho[2,1-j:1′,2′-r][1,9] dioxacyclonondecin-12,17-diamine}C51H45N3O2[α]D20=+247.7 (c 0.26, THF)Source of chirality: (S)-α-phenylethylamineAbsolute configuration: (S,S,S,S)

(12S,17S)-N12,N17-Bis[(1S)-1-phenylethyl]-{2H,8H,12H,17H-3,7-metheno-13,16-etheno-dinaphtho[2,1-j:1′,2′-r][1,9]dioxacyclonondecin-12,17-diamine}C52H46N2O2[α]D20=-62.2 (c 0.36, THF)Source of chirality: (S)-α-phenylethylamineAbsolute configuration: (S,S,S,S)

(1S,1′S)-N,N′-((1S,1′S)-1,3-Phenylenebis((2-(pyridin-2-ylmethoxy)naphthalen-1-yl)methylene))bis(1-phenyl-ethanamine)C56H50N4O2[α]D20=-54.1 (c 0.61, THF)Source of chirality: (S)-α-phenylethylamineAbsolute configuration: (S,S,S,S)