Reaction #696719

ord-90e7b13da2c544a5865bddefa72602f9

Reaction equation

CO[C@@H]1[C@H](O[Si](c2ccccc2)(c2ccccc2)C(C)(C)C)[C@@H](COS(=O)(=O)c2ccc([N+](=O)[O-])cc2)O[C@H]1n1cnc2c(NC(=O)c3ccccc3)ncnc21
14
CO[C@@H]1[C@H](O[Si](c2ccccc2)(c2ccccc2)C(C)(C)C)[C@@H](COS(=O)(=O)c2ccc([N+](=O)[O-])cc2)O[C@H]1n1cnc2c(NC(=O)c3ccccc3)ncnc21
5'-O-(4-Nitrobenzenesulfonyl)-3'-O-t-butyldiphenylsilyl-N6 -benzoyl-2'-O-methyladenosine
CO[C@@H]1[C@H](O[Si](c2ccccc2)(c2ccccc2)C(C)(C)C)[C@@H](CCl)O[C@H]1n1cnc2c(NC(=O)c3ccccc3)ncnc21
15
CO[C@@H]1[C@H](O[Si](c2ccccc2)(c2ccccc2)C(C)(C)C)[C@@H](CCl)O[C@H]1n1cnc2c(NC(=O)c3ccccc3)ncnc21
5'-chloro-5'deoxy-3'-O-t-butyldiphenylsilyl-N6 -benzoyl-2'-O-methyladenosine
[Li][N]=[N+]=[N-]
LiN3
→
CO[C@@H]1[C@H](O[Si](c2ccccc2)(c2ccccc2)C(C)(C)C)[C@@H](CN=[N+]=[N-])O[C@H]1n1cnc2c(NC(=O)c3ccccc3)ncnc21
foam
Yield 64.7%
CO[C@@H]1[C@H](O[Si](c2ccccc2)(c2ccccc2)C(C)(C)C)[C@@H](CN=[N+]=[N-])O[C@H]1n1cnc2c(NC(=O)c3ccccc3)ncnc21
5'-Azido-5'-deoxy-3'-O-t-butyldiphenylsilyl-N6 -benzoyl-2'-O-methyladenosine
Yield 64.7%

Reactants

CO[C@@H]1[C@H](O[Si](c2ccccc2)(c2ccccc2)C(C)(C)C)[C@@H](COS(=O)(=O)c2ccc([N+](=O)[O-])cc2)O[C@H]1n1cnc2c(NC(=O)c3ccccc3)ncnc21
14
CO[C@@H]1[C@H](O[Si](c2ccccc2)(c2ccccc2)C(C)(C)C)[C@@H](COS(=O)(=O)c2ccc([N+](=O)[O-])cc2)O[C@H]1n1cnc2c(NC(=O)c3ccccc3)ncnc21
5'-O-(4-Nitrobenzenesulfonyl)-3'-O-t-butyldiphenylsilyl-N6 -benzoyl-2'-O-methyladenosine
CO[C@@H]1[C@H](O[Si](c2ccccc2)(c2ccccc2)C(C)(C)C)[C@@H](CCl)O[C@H]1n1cnc2c(NC(=O)c3ccccc3)ncnc21
15
CO[C@@H]1[C@H](O[Si](c2ccccc2)(c2ccccc2)C(C)(C)C)[C@@H](CCl)O[C@H]1n1cnc2c(NC(=O)c3ccccc3)ncnc21
5'-chloro-5'deoxy-3'-O-t-butyldiphenylsilyl-N6 -benzoyl-2'-O-methyladenosine
[Li][N]=[N+]=[N-]
LiN3

Reagents

None

Solvents

CS(C)=O
DMSO

Conditions

Temperature
80°CELSIUS
Detailed conditions
See reaction.notes.procedure_details.

Workup

  1. 1
    Concentrationconcentrated in vacuo (oil pump)

Procedure

(FIG. 8C) The above mixture of 14 and 15 (3.9 g) was dissolved in dry DMSO (30 mL) and LiN3 (1.18 g, 24 mmol) was added. The reaction mixture was stirred at 80° C. overnight, then concentrated in vacuo (oil pump). After standard work up and column chromatography using 1-2% gradient MeOH in CH2Cl2 16 was obtained as a colorless foam (2.55 g), 1H NMR δ 8.92 (br s, 1H, NH), 8.72 (s, 1H, H2), 8.15 (s, 1H, H8), 8.02-7.36 (m, 15H, 3×Ph), 6.14 (d, J1',2' =3.4, 1H, H1'), 4.44 (app t, J3',4' =5.1, 1H, H3'), 4.27 (m, 1H, H4'), 4.01 (app t, J2',1' =3.4, J2',3' =4.9, 1H, H2'), 3.53 (dd, J5',4' =3.2, J5',5" =13.3, 1H, H5'), 3.37 (dd, J5",4' =4.5, J5",5' =13.3, 1H, H5"), 3.29 (s, 3H, OMe), 1.13 (s, 9H, t-Bu).

Source

DOI: 10.6084/m9.figshare.5104873.v1Patent: US05998203uspto-grants-1999_12