Water → HCID 22874345, compound

HRID 263396Notes

Reaction equation

HRID 263396 reaction equation
[C:1]([Si:5]([CH3:60])([CH3:59])[O:6][C@@H:7]1[CH2:11][C@@H:10]([CH2:12][O:13]OC)[O:9][C@@:8]1(C(C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[N:16]1[C:39]2[N:38]=[CH:37][N:36]=[C:20]([NH:21][C:22]([O:24][CH2:25][CH2:26][C:27]3[CH:32]=[CH:31][C:30]([N+:33]([O-:35])=[O:34])=[CH:29][CH:28]=3)=[O:23])[C:19]=2[N:18]=[CH:17]1)([CH3:4])([CH3:3])[CH3:2].CC1C=CC(S(O)(=O)=O)=CC=1.O>C(Cl)Cl.CO.CCOC(C)=O>[C:1]([Si:5]([CH3:60])([CH3:59])[O:6][C@@H:7]1[CH2:11][C@@H:10]([CH2:12][OH:13])[O:9][C@H:8]1[N:16]1[C:39]2[N:38]=[CH:37][N:36]=[C:20]([NH:21][C:22]([O:24][CH2:25][CH2:26][C:27]3[CH:32]=[CH:31][C:30]([N+:33]([O-:35])=[O:34])=[CH:29][CH:28]=3)=[O:23])[C:19]=2[N:18]=[CH:17]1)([CH3:3])([CH3:2])[CH3:4]

Participants

6

Reactant 3

HCID 962WaterHCID 6101p-Toluenesulfonic acidHCID 86751009HCID 86751009, compound

Product 1

HCID 22874345HCID 22874345, compoundYield 95%

Reagents, catalysts & solvents 2

HCID 8857Ethyl AcetateSolventHCID 21226129Dichloromethane methanolSolvent

Procedure

Detritylation of the fully protected monomer was accomplished by stirring a mixture of 831 mg (1 mmol) of 17 in CH2Cl2 /MeOH 4:1 (20 ml) containing 2% of TsOH×H2O for 15 minutes at r.t. The mixture was then diluted with EtOAc (130 ml), washed with saturated NaHCO3 solution (2×60 ml) and back-extracted. The organic layer was dried (MgSO4) and evaporated. The residue of the 5'-OH monomer intermediate was purified by FC (silica gel, 11.5×3 cm, gradient toluene/EtOAc 1:1+6% MeOH) to yield 530 mg (95%) of 18 as an amorphous solid. UV (MeOH): 298 (sh, 3.58), 274 (sh, 4.38), 268 (4.44). 1H-NMR ((D6)DMSO): 10.59 (s, NH); 8.70, 8.61 (2s, H--C(8), H--C(2)); 8.15 (d, 2H o to NO2), 7.61 (d, 2H m to NO2); 5.96 (s, H--C(1')); 5.15 (t, OH--C(5')); 4.74 (m, H--C(2')); 4.38 (m, H--C(4'), OCH2CH2 (6-N)); 3.73 (m, H--C (5')); 3.58 (m, H--C(5')); 3.10 (t, OCH2CH2); 2.27 (m, H--C (3')); 1.90 (m, H--C(3')); 0.82 (s, 9H, t-butyl); 0.00 (s, 2×CH3 at Si). Anal. calc. for C25H34N6O7Si (558.7): C 53.75, H 6.13, N. 15.04; found: C 53.98, H 6.12, N 14.80.

Workup

  1. washwashed with saturated NaHCO3 solution (2×60 ml)
  2. extractionback-extracted
  3. dry with materialThe organic layer was dried (MgSO4)
  4. customevaporated
  5. customThe residue of the 5'-OH monomer intermediate was purified by FC (silica gel, 11.5×3 cm, gradient toluene/EtOAc 1:1+6% MeOH)

Sources & evidence

ORD record
ord-2b4e9be6cf254c95a49c6db8bf96a3aa
Source dataset
uspto-grants-1997_07
Patent number
US05643889

Reaction notes

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