Reacción #696719

ord-90e7b13da2c544a5865bddefa72602f9

Ecuación de reacción

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
Rendimiento 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
Rendimiento 64.7%

Reactantes

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

Reactivos

Ninguno

Disolventes

CS(C)=O
DMSO

Condiciones de reacción

Temperatura
80°CELSIUS
Condiciones detalladas
See reaction.notes.procedure_details.

Tratamiento posterior

  1. 1
    Concentraciónconcentrated in vacuo (oil pump)

Procedimiento

(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).

Fuente

DOI: 10.6084/m9.figshare.5104873.v1Patente: US05998203uspto-grants-1999_12