F. Ma et al. / Tetrahedron: Asymmetry 19 (2008) 1576–1586
1585
(d, J = 7.2 Hz, 4H), 7.10–7.13 (m, 6H), 7.15 (d, J = 7.0 Hz, 2H), 7.19
(d, J = 8.9 Hz, 2H), 7.43–7.32 (m, 7H), 7.47 (t, J = 7.5 Hz, 2H), 7.58
(d, J = 8.5 Hz, 2H), 7.64 (d, J = 7.5 Hz, 2H), 7.80 (d, J = 8.9 Hz, 2H),
7.85 (d, J = 7.9 Hz, 2H). 13C NMR (125 MHz, CDCl3, ppm) d: 25.9,
55.1, 55.5, 70.3, 117.4, 123.2, 123.9, 124.0, 124.9, 126.5, 126.6,
126.9, 127.2, 127.4, 128.0, 128.1, 128.4, 129.0, 129.1, 129.3,
134.4, 135.4, 137.9, 144.7, 146.4, 155.4. IR (KBr): 3448, 3059,
7.87 (d, J = 8.2 Hz, 2H), 7.95 (t, J = 8.0 Hz, 2H), 7.96 (d, J = 3.7 Hz,
1H), 8.34 (t, J = 7.9 Hz, 2H), 8.80 (d, J = 5.6 Hz, 2H). 13C NMR
(125 MHz, CDCl3/CF3COOD-10%, ppm) d: 20.2, 56.5, 59.2, 67.1,
113.5, 114.9, 120.5, 125.4, 125.5, 126.9, 127.5, 128.9, 129.4,
129.4, 130.1, 130.4, 131.3, 132.9, 133.9, 136.4, 141.8, 147.5,
150.3, 153.3. IR (KBr): 3441, 3059, 3025, 1623, 1593, 1513, 1263,
1245 cmꢀ1; MS (EI): 810 (M+); EA for C56H50N4O2: Calcd C, 82.93;
H, 6.21; N, 6.91. Found: C, 83.16; H, 6.56; N, 6.10.
3024, 1622, 1595, 1512, 1252, 1222 cmꢀ1
;
HRMS (EI): for
58H50N2O2 calcd 806.3872, found 806.3883 (M+); EA for
58H50N2O2: Calcd C, 86.32; H, 6.24; N, 3.47. Found: C, 85.99; H,
C
C
4.4. Determination of the stoichiometry by 1H NMR titrations
(job plots)
6.40; N, 3.16.
4.2.5. (12S,17S)-N12,N17-Bis[(1S)-1-phenylethyl]-{2H,8H,12H,
17H-3,7-nitrilo-13,16-etheno-dinaphtho[2,1-j:10,20-r][1,9]
dioxacyclonondecin-12,17-diamine} (S,S,S,S)-7
The CSAs 1 and 2, (R)- and (S)-mandelic acid were separately
dissolved in CDCl3 with a concentration of 10 mM. These solutions
were distributed among 10 NMR tubes, with various amounts of
CSA 1 or 2 and acid [(R)- or (S)-mandelic acid], so that the total con-
centration of CSA and acid was 10 mM, and the molar ratio of the
CSA to the acid in the 10 tubes was 0, 0.25, 0.33, 0.43, 0.50, 0.67,
1.00, 1.50, 2.33, 4.00. The 1H NMR spectrum of each sample was re-
corded on a 500 MHz spectrometer. All recorded Job plots were
found to exhibit maxima at 0.67. This indicates that 1 and 2 form
1:2 complexes with the mandelic acids.
Mp 297–298 °C. ½a D20
ꢃ
¼ þ247:7 (c 0.26, THF). 1H NMR (500 MHz,
CDCl3, ppm): d: 1.26 (d, J = 6.3 Hz, 6H), 3.08 (br, 2H), 3.59 (q,
J = 6.4 Hz, 2H), 4.96 (br, 2H), 5.19 (br, 2H), 5.27 (br, 2H), 6.08 (br,
1H), 7.28–7.02 (m, 12H), 7.47–7.34 (m, 5H), 7.53 (br, 2H), 7.61
(br, 2H), 7.89 (d, J = 7.8 Hz, 2H), 7.94 (d, J = 8.3 Hz, 2H). 13C NMR
(125 MHz, CDCl3, ppm) d: 26.0, 55.0, 55.6, 72.7, 116.8, 121.8,
123.3, 124.1, 125.5, 126.6, 126.7, 127.2, 128.1, 128.4, 129.0,
129.4, 134.6, 136.6, 142.0, 146.4, 155.4. IR (KBr): 3440, 3062,
3023, 1621, 1593, 1509, 1253, 1213 cmꢀ1
C
C
;
HRMS (EI): for
51H45N3O2 calcd 731.3512, found 731.3520 (M+); EA for
51H45N3O2: Calcd C, 83.69; H, 6.20; N, 5.74. Found: C, 83.12; H,
4.5. Study of the discrimination ability of CSAs 1–2 towards
various acids 21–40
6.27; N, 5.70. Crystallographic data have been deposited at the
Cambridge Crystallographic Data Center (CCDC) under accession
number 617 797.
The CSAs 1 and 2, and the acids were separately dissolved in
CDCl3 with a concentration of 20 mM. Then, 0.25 mL of 1 or 2
and 0.25 mL acid were added to NMR tubes, so that the total vol-
ume was 0.5 mL and concentration of CSA and acid was 10 mM.
For some less soluble acids, such as 31–40, 1 equiv a CSA and
1 equiv of acid were mixed, to which CDCl3 was added, and the
concentration was adjusted to 10 mM. The 1H NMR spectrum of
each sample was recorded on a 500 MHz spectrometer.
4.2.6. (12S,17S)-N12,N17-Bis[(1S)-1-phenylethyl]-
{2H,8H,12H,17H-3,7-metheno-13,16-etheno-dinaphtho[2,1-j:
10,20-r] [1,9]dioxacyclonondecin-12,17-diamine} (S,S,S,S)-8
Mp 176–178 °C. ½a D20
ꢃ
¼ ꢀ62:2 (c 0.36, THF). 1H NMR (500 MHz,
CDCl3, ppm): d: 1.15 (d, J = 6.4 Hz, 6H), 3.58 (q, J = 6.29 Hz, 2H),
4.96 (d, J = 11.7 Hz, 2H), 5.27 (d, J = 11.7 Hz, 2H), 5.57 (s, 2H),
5.74 (s, 1H), 6.76 (br, 2H), 7.28–7.20 (m, 8H), 7.36–7.29 (m, 7H),
7.38 (d, J = 7.6 Hz, 2H), 7.42 (d, J = 9.2 Hz, 2H), 7.57 (d, J = 8.7 Hz,
2H), 7.87 (d, J = 8.6 Hz, 4H), 7.92 (br, 2H). 13C NMR (125 MHz,
CDCl3, ppm) d: 26.1, 54.9, 55.6, 70.6, 115.0, 123.1, 123.7, 126.3,
126.5, 126.7, 126.8, 127.3, 127.8, 128.2, 128.4, 128.8, 128.9,
134.3, 137.3, 142.5, 146.5, 154.2. IR (KBr): 3441, 3056, 3025,
1622, 1593, 1513, 1252, 1224 cmꢀ1; HRMS (EI): for C52H46N2O2
calcd 730.3559, found 730.3567 (M+); EA for C52H46N2O2: Calcd
C, 85.45; H, 6.34; N, 3.83. Found: C, 85.14; H, 6.38; N, 3.72.
4.6. Determination of enantiomeric purity of mandelic acid
Five samples containing mandelic acid with 10%, 30%, 50%, 70%,
and 95% ee, respectively (all samples were prepared by adding
0.2 equiv (not exactly) of CSA 1 or 2 in the solutions of mandelic
acid (final concentration was 10 mM in CDCl3), 3% volume of MeOD
was added to eliminate the broad signal of active protons) were
prepared and their spectra were recorded on a 500 MHz spectro-
meter. The results were calculated based on the integrations of
the NMR signals of a-H of mandelic acid isomers.
4.3. Synthesis of acyclic compound 9
Acknowledgment
A mixture of (0.628 g, 1 mmol) aminonaphthol 14a, 2-chloro-
methylpyridine hydrochloride 20 (0.489 g, 3 mmol) and K2CO3
(1.38 g 10 mmol) in 20 mL dry DMF was stirred at room tempera-
ture for 8 h. Then it was poured into 60 mL water and extracted
with toluene (20 mL ꢂ 3), and washed with water (20 mL) and
brine (20 mL). The organic phase was dried over Na2SO4, filtrated,
concentrated and purified by flash chromatography (acetone–
petroleum ether = 1: 4) (0.74 g, 91.4% yield).
This work was supported by the National Natural Science Foun-
dation of China (No. 20172008).
References
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4.3.1. (1S,10S)-N,N0-((1S,10S)-1,3-Phenylenebis((2-(pyridin-2-
ylmethoxy)naphthalen-1-yl)methylene))bis(1-phenyl-
ethanamine) (S,S,S,S)-9
Mp 161–162 °C. ½a D20
ꢃ
¼ ꢀ54:1 (c 0.61, THF). 1H NMR (500 MHz,
CDCl3/CF3COOD-10%, ppm): d: 1.65 (d, J = 6.8 Hz, 6H), 4.15 (q,
J = 6.6 Hz, 2H), 5.20 (d, J = 15.5 Hz, 2H), 5.47 (d, J = 15.5 Hz, 2H),
5.87 (s, 2H), 6.77–6.70 (m, 2H), 6.79 (d, J = 7.5 Hz, 4H), 7.01 (t,
J = 7.5 Hz, 2H), 7.18–7.08 (m, 6H), 7.27–7.30 (m, 2H), 7.42 (t,
J = 7.7 Hz, 2H), 7.44 (d, J = 7.2 Hz, 1H), 7.62 (d, J = 7.7 Hz, 2H),
6. Pirkle, W. H. J. Am. Chem. Soc. 1966, 88, 1837.
7. Many attempts have been made, using CSA to determine the enantiomeric
excess of
a-chiral carboxylic acids, but most of them cannot realize baseline