Molecules 2020, 25, 1313
13 of 21
1
43.4, 141.3, 129.4, 128.4, 127.6, 127.5, 127.0, 126.5, 125.0, 119.9, 73.2, 66.9, 62.2, 55.2, 47.4, 42.1, 27.5, 23.4;
+
+
ESI(+) MS: m/z 473.42 [M + H] ; MALDI HRMS: calculated for C H N O 473.2799, found 473.2817.
30
37
2
3
2
0
7
,3-Diaminopropanol
.21; H-NMR (300 MHz, CDCl )
.40 (t, 2H, J = 7.3, Ar Fmoc), 7.19–7.39 (m, 7H, ArH Fmoc and ArH phenyl), 5.52 (d, 1H, J = 7.8,
7
. Colorless oil (240.5 mg, 91%); TLC (diethyl ether/n-hexane 80:20, v/v): R =
f
1
δ 7.77 (d, 2H, J = 7.3, ArH Fmoc), 7.60 (d, 2H, J = 7.3, ArH Fmoc),
3
NHCO), 4.46–4.21 (m, 3H, CH and CH Fmoc), 3.63–3.92 (m, 2H, CH O), 3.55–3.62 (m, 1H, CHCH N
2
2
2
and CHNH), 2.50–2.72 (m, 3H, CH N and CHNH), 1.16 (d, 3H, J = 6.8, CH ), 1,13 (s, 9H, CH tBu);
2
3
3
1
3
C-NMR (75 MHz, CDCl3)
δ
157.1, 145.8, 144.0, 141.3, 129.4, 128.7, 127.6, 127.5, 126.4, 126.4, 125.3, 115.0,
3.2, 63.0, 53.5, 50.5, 48.8, 47.3, 27.3, 24.2; ESI(+) MS: m/z 473.35 [M + H] ; MALDI HRMS: calculated
for C H N O 473.2799, found 473.2780.
+
7
+
30
37
2
3
2
,3-Diaminopropanol 8. Colorless oil (204.3 mg, 89%); TLC (diethyl ether/n-hexane 80:20, v/v): R = 0.14;
f
1
H-NMR (300 MHz, CDCl3)
δ 7.65–7.80 (m, 2H, ArH), 7.61 (d, 2H, J = 7.0, ArH), 7.26-7.45 (m, 4H, ArH),
5
.63 (bs, 1H, NHCO), 4.38 (d, 2H, J = 6.9, CH Fmoc), 4.23 (1H, J = 6.9, CH Fmoc), 3.31–3.45 (m, 3H,
2
CH and CH O), 2.51–2.90 (m, 4H, CH N), 1.30-1.58 (m, 2H, CH CH ), 1.16 (s, 9H, CH tBu), 0.75–0.90
2
2
2
3
3
13
(
7
m, 3H, CH CH ); C-NMR (75 MHz, CDCl3) δ 156.2, 143.7, 141.3, 127.8, 127.2, 125.0, 124.8, 119.9,
3 2
+
5.6, 67.5, 52.0, 48.3, 27.2, 21.6, 11.9; ESI(+) MS: m/z 411.29 [M + H] ; MALDI HRMS: calculated for
+
C H N O 411.2642, found 411.2660.
25
35
2
3
2
=
,3-Diaminopropanol
0.24; mp 127–129 C; H-NMR (300 MHz, CDCl )
9
. Pale yellow solid (253.9 mg, 82%); TLC (diethyl ether/n-hexane 80:20, v/v): R
f
◦
1
δ
8.20–8.34 (m, 2H, SO ArH), 7.90–8.10 (m, 2H,
3
2
SO ArH), 7.76 (d, 2H, J = 7.2, ArH Fmoc), 7.55 (d, 2H, J = 7.2, ArH Fmoc), 7.33–7.44 (m, 2H, ArH Fmoc),
2
7
.20–7.32 (m, 2H, ArH Fmoc), 5.88 (bs, 1H, NHSO ), 5.32 (d, 1H, J = 7.6, NHCO), 4.35–4.49 (m, 1H,
2
CHNH), 4.29–4.35 (m, 2H, CH Fmoc), 4.10–4.19 (m, 1H, CH Fmoc), 4.00–4.09 (m, 1H, CH O), 3.73–3.87
2
2
13
(
(
5
5
m, 1H, CH O), 3.15–3.31 (m, 1H, CH N), 3.00–3.15 (m, 1H, CH N), 1.16 (s, 9H, CH tBu); C-NMR
2
2
2
3
75 MHz, CDCl3)
δ
156.4, 150.0, 145.9, 143.7, 141.3, 128.2, 127.8, 127.0, 124.9, 124.3, 120.0, 73.9, 67.1, 62.3,
+
+
0.1, 47.1, 42.1, 27.3; ESI(+) MS: m/z 554.38 [M + H] ; MALDI HRMS: calculated for C H N O S
28 32 3 7
54.1955, found 554.1938.
2
0
,3-Diaminopropanol 10. White solid (239.7 mg, 85%); TLC (diethyl ether/n-hexane 80:20, v/v): R =
f
◦
.22; mp 119–121 C; H-NMR (300 MHz, CDCl ) δ 7.68-7.80 (m, 4H, SO ArH), 7.58 (d, 2H, J = 7.4,
3 2
1
ArH Fmoc), 7.40 (t, 2H, J = 7.4, ArH Fmoc), 7.23–7.35 (m, 4H, SO ArH and ArH Fmoc), 5.32–5.48 (m,
2
2
H, NHCO and NHSO ), 4.33 (d, 2H, J = 7.2, CH Fmoc), 4.19 (t, 1H, J = 7.2, CH Fmoc), 3.75–3.85 (m,
2 2
1
H, CHNH), 3.40–3.50 (m, 2H, CH O), 3.16-3.28 (m, 1H, CH N), 3.00–3.11 (m, 1H, CH N), 2.37 (s, 3H,
2
2
2
1
3
CH tosyl), 1.15 (s, 9H, CH tBu); C-NMR (75 MHz, CDCl3)
δ
156.2, 141.2, 136.7, 129.7, 127.8, 127.5,
3
3
+
1
27.0, 125.1, 124.7, 120.0, 73.7, 66.9, 65.0, 50.3, 49.7, 47.1, 45.6, 27.3, 21.4; ESI(+) MS: m/z 523.65 [M + H] ;
+
MALDI HRMS: calculated for C H N O S 523.2261, found 523.2287.
29
35
2
5
4
.4. Methylation of 9. Synthesis of 2,3-diaminopropanol 11
Compound (100.0 mg, 0.18 mmol) was methylated with trimethyloxonium tetrafluoroborate
66.4 mg, 0.45 mmol), in the presence of DIEA (0.11 mL, 0.63 mmol), in DCM (20 mL), accordingly
9
(
to the previously published procedure [76]. Pale yellow oil (102.1 mg, quantitative); TLC (diethyl
1
ether/n-hexane 80:20 v/v) R = 0.48; H-NMR (300 MHz, CDCl )
δ 8.29–8.44 (m, 2H, SO ArH), 7.91–8.09
2
f
3
(
m, 2H, SO ArH), 7.70–7.80 (m, 2H, ArH Fmoc), 7.50-7.65 (m, 2H, ArH Fmoc), 7.31–7.42 (m, 2H, ArH
2
Fmoc), 7.23–7.31 (m, 2H, ArH Fmoc), 5.34 (d, 1H, J = 7.1, CHNH), 4.30–4.41 (m, 2H, CH Fmoc),
2
4
.12-4.28 (m, 1H, CH Fmoc), 3.75–3.97 (m, 1H, CHNH), 3.60–3.73 (m, 1H, CH O), 3.32–3.48 (m, 2H,
2
13
CH O and CH N), 3.10-3.21 (m, 1H, CH N), 2.83 (s, 3H, CH ), 1.16 (s, 9H, CH tBu); C-NMR (75 MHz,
2
2
2
3
3
CDCl3)
δ 156.1, 150.0, 143.6, 141.2, 127.7, 127.0, 125.0, 124.7, 124.4, 120.0, 73.5, 66.9, 60.5, 54.7, 51.0, 49.1,
+
+
4
7.1, 35.7, 27.2; ESI(+) MS: m/z 568.19 [M + H] ; MALDI HRMS: calculated for C H N O S 568.2112,
29 34 3 7
found 568.2133.