Tin tetrachloride → HCID 178472324, compound

HRID 2173949Notes

Reaction equation

HRID 2173949 reaction equation
[C:1]([C:3]1[CH:51]=[CH:50][C:6]2[N:7](COCC[Si](C)(C)C)[C:8]([C:10]([C:23]3[C:31]([O:32][CH3:33])=[CH:30][C:29]([CH3:34])=[C:28]4[C:24]=3[CH:25]=[CH:26][N:27]4C(OC(C)(C)C)=O)([O:15][CH:16]([F:22])[C:17]([O:19][CH2:20][CH3:21])=[O:18])[C:11]([F:14])([F:13])[F:12])=[N:9][C:5]=2[CH:4]=1)#[N:2].C(C1C=CC2N=C(C(C3C(OC)=CC(C)=C4C=3C=CN4C(OC(C)(C)C)=O)(OC(F)C(OCC)=O)C(F)(F)F)N(COCC[Si](C)(C)C)C=2C=1)#N.Cl[Sn](Cl)(Cl)Cl>ClCCl>[C:1]([C:3]1[CH:51]=[CH:50][C:6]2[NH:7][C:8]([C:10]([C:23]3[C:31]([O:32][CH3:33])=[CH:30][C:29]([CH3:34])=[C:28]4[C:24]=3[CH:25]=[CH:26][NH:27]4)([O:15][CH:16]([F:22])[C:17]([O:19][CH2:20][CH3:21])=[O:18])[C:11]([F:14])([F:12])[F:13])=[N:9][C:5]=2[CH:4]=1)#[N:2]

Participants

5

Reactant 3

HCID 24287Tin tetrachlorideHCID 86701509HCID 86701509, compoundHCID 86701510HCID 86701510, compound

Product 1

HCID 178472324HCID 178472324, compound

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Conditions

Temperature
0 °C

Procedure

To a solution of (±)-tert-butyl 4-(1-(5-cyano-1-((2-(trimethylsilyl)ethoxy)methyl)-1H-benzo[d]imidazol-2-yl)-1-(2-ethoxy-1-fluoro-2-oxoethoxy)-2,2,2-trifluoroethyl)-5-methoxy-7-methyl-1H-indole-1-carboxylate and (±)-tert-butyl 4-(1-(6-cyano-1-((2-(trimethylsilyl)ethoxy)methyl)-1H-benzo[d]imidazol-2-yl)-1-(2-ethoxy-1-fluoro-2-oxoethoxy)-2,2,2-trifluoroethyl)-5-methoxy-7-methyl-1H-indole-1-carboxylate (Example 35-E) (94 mg, 0.128 mmol) in dichloromethane (2.0 ml) at 0° C. was added SnCl4 (1.0 M in DCM, 1.279 mL, 1.279 mmol); this mixture was stirred at 0° C. for 30 min followed by warming to room temperature and stirring for 1.0 hr additional. The reaction mixture was partitioned between EtOAc/saturated sodium bicarbonate solution upon which an emulsion formed. Both layers were filtered over a plug of Celite® and then returned to the separatory funnel as two distinct layers. The organic layer was washed with brine solution, dried over sodium sulfate, and concentrated in vacuo. The resulting residue was purified with FCC eluting with ethyl acetate/heptane (0-100%) to provide the title compound. MS (ESI+) m/z 505.2 (M+H).

Workup

  1. temperatureby warming to room temperature
  2. stirringstirring for 1.0 hr additional
  3. customThe reaction mixture was partitioned between EtOAc/saturated sodium bicarbonate solution upon which an emulsion
  4. customformed
  5. filtrationBoth layers were filtered over a plug of Celite®
  6. washThe organic layer was washed with brine solution
  7. dry with materialdried over sodium sulfate
  8. concentrationconcentrated in vacuo
  9. customThe resulting residue was purified with FCC
  10. washeluting with ethyl acetate/heptane (0-100%)

Sources & evidence

ORD record
ord-771b694547de44d6ab8727e1863f16e4
Source dataset
uspto-grants-2015_06
Patent number
US09056874B2

Reaction notes

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