2,6-Dichloropurine → HCID 54507711, compound

HRID 863920Notes

Reaction equation

HRID 863920 reaction equation
C(O[CH:5]1[S:9][C@@H:8]([CH2:10][O:11][Si:12]([C:25]([CH3:28])([CH3:27])[CH3:26])([C:19]2[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=2)[C:13]2[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=2)[CH2:7][CH2:6]1)(=O)C.[Cl:29][C:30]1[N:38]=[C:37]2[C:33]([NH:34][CH:35]=[N:36]2)=[C:32]([Cl:39])[N:31]=1>>[Si:12]([O:11][CH2:10][C@@H:8]1[S:9][C@H:5]([N:36]2[CH:35]=[N:34][C:33]3[C:37]2=[N:38][C:30]([Cl:29])=[N:31][C:32]=3[Cl:39])[CH2:6][CH2:7]1)([C:25]([CH3:27])([CH3:26])[CH3:28])([C:13]1[CH:14]=[CH:15][CH:16]=[CH:17][CH:18]=1)[C:19]1[CH:20]=[CH:21][CH:22]=[CH:23][CH:24]=1

Participants

3

Reactant 2

HCID 53244122,6-DichloropurineHCID 10873398HCID 10873398, compound

Product 1

HCID 54507711HCID 54507711, compoundYield 60%

Procedure

9-[5-O-(tert-Butyldiphenylsilyl)-2,3-dideoxy-4-thio-beta-L-ribofuranosyl]-2,6-dichloropurine (69) was synthesized from the acetate 57 and 2,6-dichloropurine by the similar methodology as described for the synthesis of compound 62 in an approximate 2:3 alpha/beta anomer ratio in 60% yield. The alpha and beta anomers were separated by silica gel column chromatography. Compound 69 was treated with saturated ammonia/methanol and then deprotected with 1M tetrabutylammonium fluoride in THF to provide 2',3'-dideoxy-4'-thio-2-chloro-beta-L-adenosine (70 R'=R"=H) in 52% yield: MS m/e 286 (m+ +1); 1HNMR (DMSO-d6) delta 8.46 (s, 1H, 2-H), 7.82 (br s, 2H, NH2, D2O exchangeable), 6.10 (m, 1H, 1'-H), 5.10 (m, 1H, 5'-OH, D2O exchangeable), 3.74 (m, 1H, 4'-H), 3.60 (m, 2H, 5'-H), 2.42 (m, 2H, 2'-H), 2.13 (m, 1H, 3'-H), 2.02 (m, 1H, 3'-H).

Workup

  1. customThe alpha and beta anomers were separated by silica gel column chromatography
  2. additionCompound 69 was treated with saturated ammonia/methanol

Sources & evidence

ORD record
ord-12ef7d1739a34feba120c4b93d2a8c4f
Source dataset
uspto-grants-1996_10
Patent number
US05561120

Reaction notes

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