HCID 89998812, compound → HCID 70675010, compound

HRID 2273337Notes

Reaction equation

HRID 2273337 reaction equation
[CH:1]1[C:13]2[CH:12]([CH2:14][O:15][C:16]([NH:18][C@H:19]([C:69]([O:71]C(C)(C)C)=[O:70])[CH2:20][O:21][C:22](=[O:68])[CH2:23][CH2:24][C:25]([O:27][CH2:28][C@H:29]3[O:36][C@H:33]([O:34][CH3:35])[C@H:32]([O:37][CH2:38][CH2:39][CH2:40][CH2:41][CH2:42][CH2:43][CH2:44][CH2:45][CH2:46][CH2:47][CH2:48][CH2:49][CH2:50][CH3:51])[C@@H:31]([O:52][CH2:53][CH2:54][CH2:55][CH2:56][CH2:57][CH2:58][CH2:59][CH2:60][CH2:61][CH2:62][CH2:63][CH2:64][CH2:65][CH3:66])[C@@H:30]3[OH:67])=[O:26])=[O:17])[C:11]3[C:6](=[CH:7][CH:8]=[CH:9][CH:10]=3)[C:5]=2[CH:4]=[CH:3][CH:2]=1>C(O)(C(F)(F)F)=O>[CH:1]1[C:13]2[CH:12]([CH2:14][O:15][C:16]([NH:18][C@H:19]([C:69]([OH:71])=[O:70])[CH2:20][O:21][C:22](=[O:68])[CH2:23][CH2:24][C:25]([O:27][CH2:28][C@H:29]3[O:36][C@H:33]([O:34][CH3:35])[C@H:32]([O:37][CH2:38][CH2:39][CH2:40][CH2:41][CH2:42][CH2:43][CH2:44][CH2:45][CH2:46][CH2:47][CH2:48][CH2:49][CH2:50][CH3:51])[C@@H:31]([O:52][CH2:53][CH2:54][CH2:55][CH2:56][CH2:57][CH2:58][CH2:59][CH2:60][CH2:61][CH2:62][CH2:63][CH2:64][CH2:65][CH3:66])[C@@H:30]3[OH:67])=[O:26])=[O:17])[C:11]3[C:6](=[CH:7][CH:8]=[CH:9][CH:10]=3)[C:5]=2[CH:4]=[CH:3][CH:2]=1

Participants

3

Reactant 1

HCID 89998812HCID 89998812, compound

Product 1

HCID 70675010HCID 70675010, compoundYield 82.4%

Reagents, catalysts & solvents 1

HCID 6422Trifluoroacetic acidSolvent

Procedure

Conjugate 23 (0.2 g, 0.17 mmol) was dissolved in TFA/wet CH2Cl2(1/5, v/v, 4 mL) and the resulting mixture was stirred for 2 h at rt. After that, the volatiles were evaporated under the reduced pressure, the residue was diluted with CH2Cl2 (5 mL) and neutralized with triethylamine (until pH ˜7). The volatiles were removed under the reduced pressure and the residue was purified by column chromatography on silica gel (ethyl acetate/hexane 1/1, v/v) to obtain the title compound 24 (0.13 g, 0.14 mmol) as a white amorphous solid in 81% yield. Analytical data for 24: Rf=0.58 (methanol/ethyl acetate, 1.5/8.5, v/v); [α]D26+34.9° (c=1.0, CHCl3); 1H NMR (500 MHz, CDCl3/(CD3)2SO, 2/1, v/v): δ, 0.78 (t, 6H, 2×CH3), 1.45 (br. s, 40H, 20×CH2), 1.47 (m, 4H, 2×CH2), 2.5 (m, 4H, 2×CH2), 3.10 (dd, 1H, J2,3=9.4 Hz, H-2), 3.22-3.33 (m, 7H), 3.41-3.51 (m, 3H), 3.55 (m, 1H, H-5), 3.64 (t, 2H, J=6.7 Hz), 4.14-4.32 (m, 7H), 4.42 (d, 1H, J=9.5 Hz), 4.63 (d, 1H, J1,2=3.2 Hz, H-1), 6.52 (br. s, 1H, Ser-NH), 7.22-7.82 (m, 8H, aromatic) ppm; 13C NMR (125 MHz, CDCl3/(CD3)2SO, 2/1, v/v): δ, 13.6, 21.9, 25.4, 25.5, 28.6, 28.8, 28.9, 29.0, 29.5 (×2), 31.2, 39.0, 39.2, 39.3, 39.5, 39.7, 39.8 (×2), 39.9, 40.0, 40.1, 46.6, 54.3, 63.4, 65.6, 69.2, 69.4, 70.6, 72.7, 79.6, 80.7, 97.3, 119.4, 124.6, 124.8, 126.6, 127.1, 140.1, 143.4, 155.4, 171.3, 171.6, 178.3, 178.7 ppm; HR FAB MS [M+Na]+ calcd for C57H89NO13Na 1018.6232. found 1018.6182.

Workup

  1. customAfter that, the volatiles were evaporated under the reduced pressure
  2. additionthe residue was diluted with CH2Cl2 (5 mL)
  3. customThe volatiles were removed under the reduced pressure
  4. customthe residue was purified by column chromatography on silica gel (ethyl acetate/hexane 1/1

Sources & evidence

ORD record
ord-5f80bee406cc4964806f421f052ae10d
Source dataset
uspto-grants-2015_09
Patent number
US09120838B2

Reaction notes

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