K. Sidoryk et al. / Journal of Molecular Structure 1153 (2018) 135e148
147
2H); 13C NMR (CDCl3, 150 MHz)
136.7 (C), 136.1 (C), 128.57, 128.56, 128.55, 128.3, 128.26, 128.2,
127.9, 127.8, 127.3, 127.1, 122.9, 115.9, 114.2, 113.7, 71.3 (CH2), 70.9
(CH2), 66.2 (CH2).
d
166.9, 151.1, 148.9, 144.9, 136.8 (C),
CH3OH to afford a white solid (1.96 g, 84%); HPLC purity 97.00%;
20
m.p. 88e90 ꢀC; [
500 MHz)
a]
¼ - 44.6 (c 0.75, CHCl3); 1H NMR (CDCl3;
D
d
7.44e7.25 (m, 15H), 6.81e6.80 (m, 2H), 6.64e6.63 (m,
1H), 5.13e5.09 (m, 6H), 4.43 (m, 1H), 3.01 (dd, 1H, J ¼ 4.5 Hz,
J ¼ 14 Hz), 2.89 (dd, 1H, J ¼ 6.4 Hz, J ¼ 14 Hz); 13C NMR (CDCl3,
4.11. (3E)-4-[3,4-bis(phenylmethoxy)phenyl]-3-buten-2-one 5
125 MHz) d 173.8, 148.7, 148.0, 137.4, 137.2, 135.0, 129.4, 128.7, 128.6,
128.5, 128.4, 127.7, 127.4, 127.3, 122.5, 116.6, 115.1, 71.4, 71.2 (CH2),
67.3 (CH2), 39.9 (CH2); HR-MS (ESI) calc. for C30H28O5Na [MþNa]þ:
491.1834. Found: 491.1837.
m.p. 99e101 ꢀC; 1H NMR (CDCl3; 600 MHz)
d 7.45e7.44 (m, 4H),
7.40e7.35 (m, 5H), 7.32e7.29 (m, 2H), 7.13 (d, 1H, J ¼ 2 Hz), 7.07 (dd,
1H, J ¼ 2 Hz, J ¼ 8.4 Hz), 6.92 (d, 1H, J ¼ 8.4 Hz), 6.52 (d, 1H,
J ¼ 16 Hz), 5.19e5.17 (m, 4H), 2.33 (s, 3H); 13C NMR (CDCl3,
4.15. Benzyl (2R)-hydroxy-3-(3,4-dibenzyloxyphenyl)-propionate
7b
150 MHz) d 198.3, 151.3, 149.0, 143.3, 136.8, 136.6, 128.5, 127.9, 127.7,
127.3, 127.1, 125.4, 123.2, 114.2, 113.7, 71.3 (CH2), 70.9 (CH2), 27.3;
HR-MS (ESI) calc. for C24H23O3 [MþH]þ: 359.1647. Found: 359.1649.
To the ice-cooled solution of 6b (7.0 g, 14.45 mmol) in anhydrous
DCM (70 mL), Et3SiH (23.1 mL, 144.46 mmol) and TFA (12.92 mL,
173.4 mmol) were added dropwise and stirred for 30 min at 0 ꢀC.
Next, the whole mixture was stirred at room temperature until no
more starting material was detected on TLC (approx. 6 h). The so-
lution was evaporated to dryness, then CH3OH was added and
evaporated once more to dryness. The residue was crystallized from
4.12. Benzyl (2S, 3R)-2,3-dihydroxy-3-(3,4-dibenzyloxyphenyl)-
propionate 6a
AD-mix b (16 g) and methanosulponamide (1.1 g) were added to
the suspension of 4 (5.0 g, 11.09 mmol) in the mixture of acetone/
acetonitile/water (3:3:1, v/v, 80 mL). The suspension was stirred for
24 h at room temperature. The reaction was quenched with the
saturated solution of Na2SO3, concentrated, and extracted with
ethyl acetate. The solvents were evaporated under diminished
pressure. Column chromatography of the residue (hexane e ethyl
acetate, 6:1 / 1:1) afforded the title compound as a white solid
CH3OH to afford a white solid (4 g, 60%); HPLC purity 94.91%; m.p.
20
86e89 ꢀC; [
d
a]
¼ þ 44.8 (c 0.75, CHCl3); 1H NMR (CDCl3; 500 MHz)
D
7.44e7.28 (m, 15H), 6.81e6.79 (m, 2H), 6.64e6.62 (dd, 1H,
J ¼ 2 Hz, J ¼ 8.1 Hz), 5.12e5.08 (m, 6H), 4.42 (m, 1H), 3.01 (dd, 1H,
J ¼ 4.5 Hz, J ¼ 14 Hz), 2.89 (dd, 1H, J ¼ 6.4 Hz, J ¼ 14 Hz); 13C NMR
(CDCl3, 125 MHz)
d 173.8, 148.7, 148.0, 137.4, 137.3, 135.0, 129.4,
(3.1 g, 58%); HPLC purity 99.22%; m.p. 86e88 ꢀC; mp. 97e100 ꢀC
128.7, 128.6, 128.5, 128.4, 127.7, 127.4, 127.3, 122.5, 116.6, 115.1, 71.4,
71.2 (CH2), 67.3 (CH2), 39.9 (CH2); HR-MS (ESI) calc. for C30H28O5Na
[MþNa]þ: 491.1834. Found: 491.1819.
20
[20]; [
d
a]
¼ - 1.2 (c 0.75, CHCl3); 1H NMR (CD3OD; 500 MHz)
D
7.44e7.42 (m, 4H), 7.35e7.31 (m, 9H), 7.24e7.23 (m, 2H), 7.08 (d,
1H, J ¼ 1.5 Hz), 6.90e6.89 (m, 2H), 5.11e5.04 (m, 6H), 4.85 (d, 1H,
J ¼ 4.5 Hz), 4.27 (d, 1H, J ¼ 4.5 Hz); 13C NMR (CD3OD, 125 MHz)
4.16. 3-(3,4-dihydroxyphenyl)-(S)-lactic acid S-DSS
d
173.0, 149.3, 149.0, 137.7, 137.6, 135.8, 134.4, 128.94, 128.9, 128.8,
128.7, 128.6, 128.3, 128.0, 127.8, 120.4, 115.3, 114.2, 76.3, 75.1, 71.8,
67.4.
The solution of 7a (0.5 g, 1.06 mmol) and 10% Pd/C (100 mg) in
the mixture of THF/C2H5OH (1:1, v/v, 30 mL) was placed under
hydrogen and stirred for 1 h at room temperature. The mixture was
filtered through a Celite which was washed with ethanol (5 mL).
The filtrate was concentrated in vacuo at 40 ꢀC to give brown oil.
Column chromatography of the crude product (chloroform e
methanol, 10:1 /1:1) was performed to afford the title compound
4.13. Benzyl (2R, 3S)-2,3-dihydroxy-3-(3,4-dibenzyloxyphenyl)-
propionate 6b
AD-mix a (33 g) and methanosulponamide (2.2 g) were added to
the suspension of 4 (10.0 g, 22.19 mmol) in the mixture of acetone/
acetonitile/water (3:3:1, v/v, 160 mL). The suspension was stirred
for 24 h at room temperature. The reaction was quenched with the
saturated solution of Na2SO3, concentrated, and extracted with
ethyl acetate. The solvents were evaporated under diminished
pressure. Column chromatography of the residue (hexane e ethyl
acetate, 6:1 / 1:1) afforded the title compound as a white solid
as yellow oil. The lyophilization of oil afforded the product as yel-
20
low foam (0.201 g, 95%); HPLC purity 94.91%; [
a
]
¼ - 24.0 (c 0.5,
D
H2O); 1H NMR (D2O; 600 MHz)
d
6.86 (d, 1H, J ¼ 8.1 Hz), 6.82 (d, 1H,
J ¼ 2 Hz), 6.72 (dd, 1H, J ¼ 2 Hz, J ¼ 8.1 Hz), 4.39e4.36 (m, 1H), 3.01
(dd, 1H, J ¼ 4.5 Hz, J ¼ 14.2 Hz), 2.83 (dd, 1H, J ¼ 7.6 Hz, J ¼ 14.2 Hz);
13C NMR (D2O, 150 MHz)
d 181.1, 146.4, 145.3, 132.6, 124.5, 119.8,
118.8, 74.7, 41.7; HR-MS (ESI) calc. for C9H9O5 [M ꢁ H]-: 197.0450.
(7.37 g, 69%); HPLC purity 99.72%; m.p. 84e89 ꢀC; 88e91 ꢀC [20];
Found: 197.0454.
20
[
a]
¼ þ 1.2 (c 0.75, CHCl3); 1H NMR (CD3OD; 500 MHz)
D
d
7.42e7.41 (m, 4H), 7.33e7.25 (m, 9H), 7.20e7.18 (m, 2H), 7.10 (d,
4.17. 3-(3,4-dihydroxyphenyl)-(R)-lactic acid R-DSS
1H, J ¼ 1.9 Hz), 6.93 (d, 1H, J ¼ 8.3 Hz), 6.85 (dd, 1H, J ¼ 0.4 Hz,
J ¼ 1.9 Hz), 5.07e4.97 (m, 6H), 4.81 (d, 1H, J ¼ 4.9 Hz), 4.23 (d, 1H,
The solution of 7b (0.4 g, 0.854 mmol) and 10% Pd/C (80 mg) in
the mixture of THF/C2H5OH (1:1, v/v, 20 mL) was placed under
hydrogen and stirred for 1.5 h at room temperature. The mixture
was filtered through a Celite which was washed with ethanol
(5 mL). The filtrate was concentrated in vacuo at 40 ꢀC to give
brown oil. Column chromatography of the crude product (chloro-
form e methanol, 10:1 / 1:1) was performed to afford the title
J ¼ 4.9 Hz); 13C NMR (CD3OD, 125 MHz)
d 173.6, 150.1, 149.8, 137.8,
138.7, 137.0, 135.5, 129.5, 129.42, 129.41, 129.2, 128.8, 128.7, 128.6,
121.2, 115.9, 115.1, 77.3, 76.1, 72.3, 67.6.
4.14. Benzyl (2S)-hydroxy-3-(3,4-dibenzyloxyphenyl)-propionate
7a
compound as yellow oil. The solid product was precipitated from
20
To the ice-cooled solution of 6a (2.41 g, 4.97 mmol) in anhydrous
DCM (25 mL), Et3SiH (7.94 mL, 49.74 mmol) and TFA (4.44 mL,
59.64 mmol) were added dropwise and stirred for 30 min at 0 ꢀC.
Next, the whole mixture was stirred at room temperature until no
more starting material was detected on TLC (approx. 5 h). The so-
lution was evaporated to dryness, then CH3OH was added and
evaporated once more to dryness. The residue was crystallized from
hexanes (0.201 g, 95%); HPLC purity 96.33%; [
a]
¼ þ 25.4 (c 0.5,
D
H2O); 1H NMR (D2O; 600 MHz)
d
6.88 (d, 1H, J ¼ 8.1 Hz), 6.84 (d, 1H,
J ¼ 2 Hz), 6.73 (dd, 1H, J ¼ 2 Hz, J ¼ 8.1 Hz), 4.29e4.25 (m, 1H), 3.00
(dd, 1H, J ¼ 4.2 Hz, J ¼ 14.2 Hz), 2.79 (dd, 1H, J ¼ 7.7 Hz, J ¼ 14.2 Hz);
13C NMR (D2O, 150 MHz)
d 182.3, 146.1, 144.8, 132.9, 124.2, 119.5,
118.5, 75.3, 41.7; HR-MS (ESI) calc. for C9H9O5 [M ꢁ H]-: 197.0450.
Found: 197.0455.