Cesium carbonate → HCID 69813110, compound

HRID 1809452Notes

Reaction equation

HRID 1809452 reaction equation
Br[C:2]1[N:6]2[C:7]([C:11]([O:13][CH3:14])=[O:12])=[CH:8][CH:9]=[CH:10][C:5]2=[N:4][C:3]=1[C:15]1[CH:20]=[CH:19][C:18]([C:21]#[N:22])=[CH:17][CH:16]=1.C([O-])([O-])=O.[Cs+].[Cs+].F[B-](F)(F)F.C([PH+](C(C)(C)C)C(C)(C)C)(C)(C)C.C([Sn](CCCC)(CCCC)/[CH:52]=[CH:53]\[O:54][CH2:55][CH3:56])CCC.C([O-])(O)=O.[Na+]>CN(C=O)C.C(Cl)Cl>[C:21]([C:18]1[CH:19]=[CH:20][C:15]([C:3]2[N:4]=[C:5]3[CH:10]=[CH:9][CH:8]=[C:7]([C:11]([O:13][CH3:14])=[O:12])[N:6]3[C:2]=2/[CH:52]=[CH:53]/[O:54][CH2:55][CH3:56])=[CH:16][CH:17]=1)#[N:22]

Participants

8

Reactant 5

HCID 10796Cesium carbonateHCID 516892Sodium BicarbonateHCID 2734635Tri-tert-butylphosphine tetrafluoroborateHCID 5706773cis-1-Ethoxy-2-(tri-n-butylstannyl)ethyleneHCID 68639473HCID 68639473, compound

Product 1

HCID 69813110HCID 69813110, compoundYield 74%

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideSolventHCID 6344DichloromethaneSolvent

Conditions

Temperature
70 °C

Procedure

To a degassed solution of (A3) in DMF (0.1 M), Cs2CO3 (1.1 eq.), tris(dibenzenzylideneacetone)dipalladium(0) (0.05 eq.), tri-t-butylphosphonium tetrafluoroborate (0.15 eq.) and tributyl[(Z)-2-ethoxyvinyl]stannane (2.0 eq.) were added at RT and the reaction mixture was heated to 70° C. for 12 h. After cooling down, the solvent was reduced in vacuo and the residue partioned between sat. aq. NaHCO3 and DCM. The aqueous phase was separated and extracted several times with DCM. The combined organic extracts were washed with brine and dried (Na2SO4). Evaporation of the solvent gave a residue which was purified by flash column on silica using a gradient of EtOAc/Petroleum ether from 30:70 to 50:50 to yield (74%) the title compound as a yellow oil, it is a mixture of regioisomers (cis/trans=4:1). 1H NMR (300 MHz, CDCl3, 300K) δ 8.10 (2H, d, J=8.3 Hz), 7.90 (1H, d, J=8.7 Hz), 7.70 (2H, d, J=8.3 Hz), 7.40 (1H, d, J=6.4 Hz), 7.35-7.25 (1H, m), 6.32 (1H, d, J=6.7 Hz), 5.65 (1H, d, J=6.4 Hz), 3.97 (3H, s), 3.74 (2H, q, J=7.0 Hz), 1.03 (3H, t, J=7.0 Hz). MS (ES+) C20H17N3O3 requires: 347, found: 348 (M+H)+.

Workup

  1. temperatureAfter cooling down
  2. customThe aqueous phase was separated
  3. extractionextracted several times with DCM
  4. washThe combined organic extracts were washed with brine
  5. dry with materialdried (Na2SO4)
  6. customEvaporation of the solvent
  7. customgave a residue which
  8. customwas purified by flash column on silica using a gradient of EtOAc/Petroleum ether from 30:70 to 50:50

Sources & evidence

ORD record
ord-b2ff71b2459d41ebb9b14f1068ede6ed
Source dataset
uspto-grants-2013_01
Patent number
US08362030B2

Reaction notes

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