Sodium Carbonate → HCID 145857603, compound

HRID 2216165Notes

Reaction equation

HRID 2216165 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5]([NH:8][CH3:9])=[CH:4][C:3]=1[CH3:10].C1(P(C2CCCCC2)C2C=CC=CC=2C2C=CC=CC=2)CCCCC1.B([O-])[O-].[C:39]([O:43][C:44](=[O:65])[NH:45][C:46]([C:48]1[S:49][C:50]([S:63][CH3:64])=[C:51]([S:53]([C:56]2[CH:61]=[CH:60][CH:59]=[C:58](Br)[CH:57]=2)(=[O:55])=[O:54])[CH:52]=1)=[NH:47])([CH3:42])([CH3:41])[CH3:40].C([O-])([O-])=O.[Na+].[Na+]>O1CCOCC1.C(O)C.C1(C)C=CC=CC=1.C([O-])(=O)C.[Pd+2].C([O-])(=O)C.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[C:39]([O:43][C:44](=[O:65])[NH:45][C:46](=[NH:47])[C:48]1[S:49][C:50]([S:63][CH3:64])=[C:51]([S:53]([C:56]2[CH:61]=[C:60]([C:2]3[CH:7]=[CH:6][C:5]([NH:8][CH3:9])=[CH:4][C:3]=3[CH3:10])[CH:59]=[CH:58][CH:57]=2)(=[O:55])=[O:54])[CH:52]=1)([CH3:42])([CH3:40])[CH3:41]

Participants

11

Reactant 5

HCID 10340Sodium CarbonateHCID 27342162-(Dicyclohexylphosphino)biphenylHCID 218865734-Bromo-N,3-dimethylbenzenamineHCID 145857672tert-butyl N-[4-(3-bromophenyl)sulfonyl-5-methylsulfanylthiophene-2-carboximidoyl]carbamateHCID 178514824HCID 178514824, compound

Product 1

HCID 145857603HCID 145857603, compoundYield 62%

Reagents, catalysts & solvents 5

HCID 167845palladium(II) acetateCatalystHCID 178418397HCID 178418397, compoundCatalystHCID 702EthanolSolventHCID 1140TolueneSolventHCID 312751,4-DioxaneSolvent

Procedure

The procedure in Example 294: step e was followed using (4-bromo-3-methyl-phenyl)-methyl-amine ((Example 262: step a) 600 mg, 3 mmol), palladium acetate (34 mg, 0.15 mmol), and 2-(dicyclohexylphosphino)biphenyl (210 mg, 0.6 mmol) in dioxane (20 mL). Analogous workup yielded the crude pinacolboronate ester (720 mg, 98%) which was used without further purification. Following the procedure in Example 294: step f the crude boronate (540 mg, 2.18 mmol) was reacted with {[4-(3-bromo-benzenesulfonyl)-5-methylsulfanyl-thiophen-2-yl]-imino-methyl}-carbamic acid tert-butyl ester ((Example 27: step c) 715 mg, 1.46 mmol), aq Na2CO3 (2M, 4.4 mL, 8.8 mL), and Pd(PPh3)4 (407 mg, 0.37 mmol) in ethanol (4.4 mL) and toluene (8.8 mL). Analogous workup and SiO2 flash column chromatography yielded the title compound (482 mg, 62%) as a yellow glass. 1H-NMR (CDCl3): δ 8.0 (s, 1H), 7.95 (m, 1H), 7.90 (m, 1H), 7.55 (m, 1H), 7.51 (m, 1H), 7.05 (m, 1H), 6.53 (m, 2H), 2.9 (s, 3H), 2.56 (s, 3H), 2.56 (s, 3H), 2.22 (s, 3H), 1.52 (s, 9H).

Workup

  1. customAnalogous workup yielded the crude pinacolboronate ester (720 mg, 98%) which
  2. customwas used without further purification

Sources & evidence

ORD record
ord-04901857444a45e2930c640c94d8eef4
Source dataset
uspto-grants-2006_09
Patent number
US07109354B2

Reaction notes

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