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Organic & Biomolecular Chemistry
DOI: 10.1039/C6OB01286H
ARTICLE
Journal Name
7
0.0, 70.4, 70.5, 70.55, 70.58, 81.5, 169.6. HRMS (ESI) calcd for 119.9, 125.2, 127.0, 127.6, 141.3, 144.0, 156.7, 169.7. HRMS (ESI)
+
26)/2 [(M+2NH
2+
) ] 624.8910, found 624.8865.
+
+
calcd for C37H55NNaO12 [(M+Na) ] 728.3616, found 728.3620.
(
C
54
H
115
N
5
O
4
Compound 5a. Compound 4a (600.1 mg, 2.1 mmol) was dissolved Compound 5f was prepared from 4f by following the same
1
in THF (50 mL) and then triphenylphosphine (816 mg, 3.1 mmol) procedure for 5a as yellowish oil (280.0 mg, 80%). H NMR (400
was added and the mixture was stirred for 5 h at 25 °C. H
2 3
O (190 ꢁL, MHz, CDCl ) δ 1.47 (s, 9H), 3.39-3.43 (m, 2H), 3.56-3.72 (m, 34H),
1
0.5 mmol) was then added to the reaction mixture and the mixture 4.02 (s, 2H), 4.23 (t, J = 6.8 Hz, 1H), 4.39 (d, J = 7.2 Hz, 2H), 7.30-
1
was stirred for an additional hour. The reaction mixture was 7.77 (m, 8H). C NMR (100 MHz, CDCl
3
3
) δ 28.0, 40.8, 47.2, 66.4,
concentrated under vacuum and the residue was purified by flash 68.9 70.0, 70.2, 70.4, 70.5, 70.6, 81.4, 119.8, 125.0, 127.0, 127.6,
+
chromatography on silica gel to give the crude product. Then the 141.2, 143.9, 156.5, 169.6. HRMS (ESI) calcd for C39H60NO13
+
crude product was dissolved in THF (30 mL) and added to a mixture [(M+H) ] 750.4059, found 750.4097; calcd for C39H59NNaO13
+
+
3 2
of saturated NaHCO (147.7 mg, 1.8 mmol in 1.5 mL H O ) at 0 °C. [(M+Na) ] 772.3879, found 772.3941.
The reaction mixture was then slowly added a solution of 9- Compound 5g was prepared from 4g by following the same
1
fluorenylmethyl chloroformate (452.2 g, 1.8 mmol) in THF ( 20 mL) procedure for 5a as yellowish oil (870.0 mg, 55%). H NMR (400
3
over 1 h. The reaction mixture was stirred at 25 °C for 4 h. Brine MHz, CDCl ) δ 1.47 (s, 9H), 3.38-3.42 (m, 2H), 3.56-3.72 (m, 38H),
(
200 mL) was added to quench the reaction. EtOAc (100 mL) was 4.02 (s, 2H), 4.23 (t, J = 6.8 Hz, 1H), 4.39 (d, J = 7.2 Hz, 2H), 7.29-
1
added to the reaction mixture and the organic layer was collected. 7.77 (m, 8H). C NMR (100 MHz, CDCl
3
3
) δ 28.0, 40.7, 47.2, 66.4,
The aqueous layer was extracted with EtOAc (300 mL, 3 times). 68.9, 70.1, 70.2, 70.4, 70.5, 70.6, 81.5, 119.9, 125.1, 127.0, 127.6,
+
The combined organic layer was dried over anhydrous Na
concentrated under vacuum, purified by chromatography on silica [(M+Na) ] 816.4141, found 816.4149.
gel with EtOAc/PE (1/3) as eluents to give 5a (690.0 mg, 68% yield) Compound 5h was prepared from 4h by following the same
2
SO
4
,
141.2, 144.0, 156.6, 169.6. HRMS (ESI) calcd for C41H63NNaO14
+
1
1
as light yellow oil. H NMR (400 MHz, CDCl
3
) δ 1.45 (s, 9H), 3.39- procedure for 5a as yellowish oil (410.0 mg, 80%). H NMR (400
.43 (m, 2H), 3.58 (t, J = 4.8 Hz, 2H), 3.65-3.72 (m, 8H), 4.00 (s, MHz, CDCl ) δ 1.47 (s, 9H), 3.40 (t, J = 5.2 Hz, 2H), 3.56-3.72 (m,
H), 4.23 (t, J = 6.8 Hz, 1H), 4.38 (d, J = 7.2 Hz, 2H), 7.30-7.77 (m, 42H), 4.02 (s, 2H), 4.23 (t, J = 6.8 Hz, 1H), 4.39 (d, J = 7.2 Hz, 2H),
3
2
8
7
1
4
5
5
3
13
13
H). C NMR (100 MHz, CDCl
3 3
) δ 28.2, 41.0, 47.3, 66.7, 69.0, 7.30-7.77 (m, 8H). C NMR (100 MHz, CDCl ) δ 28.0, 40.8, 47.2,
0.2, 70.3, 70.6, 70.7, 81.8, 120.0, 125.2, 127.1, 127.7, 141.4, 144.1, 66.4, 68.9, 70.0, 70.2, 70.4, 70.5, 70.6, 81.5, 119.9, 125.1, 127.0,
+
56.7, 169.7. HRMS (ESI) calcd for
+
[(M+H) ] 127.6, 141.2, 143.9, 156.6, 169.6. HRMS (ESI) calcd for
C
27
H
36NO
+
7
+
) ]
+
+
15 [(M+NH
+
) ] 855.4849, found 855.4843; calcd for
+
67NNaO15 [(M+Na) ] 860.4403, found 860.4418.
86.2486, found 486.2504; calcd for C27
H
39
N
2
O
7
[(M+NH
4
C
C
43
43
H
71
N
2
O
4
+
+
03.2752, found 503.2766; calcd for C27
08.2306, found 508.2333.
H
35NNaO
7
[(M+Na) ]
H
Compound 5i was prepared from 4i by following the same
1
procedure for 5a as yellowish oil (14.0 g, 80%). H NMR (400
Compound 5b was prepared from 4b by following the same
1
procedure for 5a as yellowish oil (1.0 g, 70%). H NMR (400 MHz,
MHz, CDCl
3
) δ 1.47 (s, 9H), 3.38-3.42 (m, 2H), 3.56-3.73 (m,
CDCl
3
) δ 1.45 (s, 9H), 3.39-3.42 (m, 2H), 3.57 (t, J = 4.8 Hz, 2H),
46H), 4.02 (s, 2H), 4.22 (t, J = 6.8 Hz, 1H), 4.40 (d, J = 6.8 Hz,
1
3
3.64-3.68 (m, 12H), 3.99 (s, 2H), 4.23 (t, J = 6.8 Hz, 1H), 4.39 (d, J
3
2H), 7.30-7.77(m, 8H). C NMR (100 MHz, CDCl ) δ 28.0, 40.7,
13
=
7.2 Hz, 2H), 7.29-7.77 (m, 8H). C NMR (100 MHz, CDCl
3
) δ
47.1, 66.3, 68.8, 69.9, 70.1, 70.36, 70.40, 70.5, 81.3, 119.8, 125.0,
2
8.1, 40.9, 47.3, 66.5, 68.9, 70.1, 70.3, 70.5, 70.6, 70.7, 81.6, 119.9,
126.9, 127.5, 141.1, 143.8, 156.4, 169.5. HRMS (ESI) calcd for
+
+
16 [(M+NH
125.1, 127.0, 127.6, 141.3, 144.0, 156.6, 169.6. HRMS (ESI) calcd
+
C
45
H
75
N
2
O
4
) ] 899.5111, found 899.5133.
+
8
forin C29H39NNaO [(M+Na) ] 552.2568, found 552.2542.
Compound 5j was prepared from 4j by following the same
1
Compound 5c was prepared from 4c by following the same procedure for 5a as yellowish oil (510.0 mg, 62%). H NMR (400
1
procedure for 5a as yellowish oil (350.0 mg, 73%). H NMR (400 MHz, CDCl
MHz, CDCl ) δ 1.47 (s, 9H), 3.38-3.42 (m, 2H), 3.57 (t, J = 5.2 Hz, 4.02 (s, 2H), 4.23 (t, J = 6.8 Hz, 1H), 4.39 (d, J = 7.2 Hz, 2H), 7.29-
H), 3.63-3.68 (m, 20H), 4.00 (s, 2H), 4.23 (t, J = 6.8 Hz, 1H), 4.39 7.77 (m, 8H). C NMR (100 MHz, CDCl
d, J = 6.8 Hz, 2H), 7.30-7.77 (m, 8H). 68.9, 70.1, 70.2, 70.4, 70.5, 70.6, 81.5, 119.8, 125.1, 127.0, 127.6,
Compound 5d was prepared from 4d by following the same 141.2, 144.0, 156.6, 169.6. HRMS (ESI) calcd for C53
3
) δ 1.47 (s, 9H), 3.38-3.42 (m, 2H), 3.56-3.73 (m, 62H),
3
1
3
2
3
) δ 28.0, 40.7, 47.2, 66.4,
(
+
H87NNaO20
1
+
procedure for 5a as yellowish oil (250.0 mg, 79%). H NMR (400 [(M+Na) ] 1080.5714, found 1080.5700.
MHz, CDCl ) δ 1.47 (s, 9H), 3.38-3.42 (m, 2H), 3.57 (t, J = 4.8 Hz, Compound 5k was prepared from 4k by following the same
H), 3.62-3.69 (m, 24H), 4.01 (s, 2H), 4.22 (t, J = 6.8 Hz, 1H), 4.40 procedure for 5a as yellowish wax (8.7 g, 80%). H NMR (400
3
1
2
1
3
(
d, J = 6.8 Hz, 2H), 7.30-7.77 (m, 8H). C NMR (100 MHz, CDCl
3
)
3
MHz, CDCl ) δ 1.40 (s, 9H), 3.30-3.34 (m, 2H), 3.49-3.66 (m, 94H),
δ 28.1, 40.9, 47.3, 66.5, 69.0, 70.1, 70.3, 70.5, 70.6, 70.7, 81.5, 3.95 (s, 2H), 4.15 (t, J = 6.8 Hz, 1H), 4.32 (d, J = 6.8 Hz, 2H), 7.22-
1
19.9, 125.1, 127.0, 127.6, 141.3, 144.0, 156.6, 169.7. HRMS (ESI) 7.70 (m, 8H). C NMR (100 MHz, CDCl
3
1
3
) δ 27.5, 40.2, 46.6, 65.6,
68.3, 69.3, 69.6, 69.9, 80.7, 119.3, 124.5, 126.5, 127.0, 140.6, 143.4,
+
calcd for C35H51NNaO11 [(M+Na) ] 684.3354, found 684.3358.
+
2+
2 28
Compound 5e was prepared from 4e by following the same 156.0, 169.0. HRMS (ESI) calcd for (C69H119NNa O )
1
2+
procedure for 5a as yellowish oil (700.0 mg, 66%). H NMR (400 [(M+2Na) ] 727.8852, found 727.8953.
MHz, CDCl ) δ 1.47 (s, 9H), 3.39-3.42 (m, 2H), 3.57 (t, J = 4.8 Hz, Compound 6a. A solution of compound 5i (11.5 g, 13.0 mmol),
H), 3.61-3.72 (m, 28H), 4.01 (s, 2H), 4.23 (t, J = 6.8 Hz, 1H), 4.39 anisole (2.8 mL, 26.0 mmol) and TFA (16.1 mL) in DCM (150 mL)
3
2
1
3
(
d, J = 7.2 Hz, 2H), 7.29-7.77 (m, 8H). C NMR (100 MHz, CDCl
3
)
was stirred at 25 °C over night. After concentrated under vaccum,
δ 28.1, 40.9, 47.3, 66.5, 69.0, 70.1, 70.2, 70.49, 70.53, 70.7, 81.6, the residue was dissolved in ether (100 mL) and washed with water
(
100 mL). The organic layer was discarded and the aqueous layer
6
| J. Name., 2012, 00, 1-3
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