Potassium Carbonate → HCID 22593643, compound

HRID 1767453Notes

Reaction equation

HRID 1767453 reaction equation
C(=O)([O-])[O-].[K+].[K+].[SH:7][CH2:8][CH2:9][NH:10][C:11](=[O:17])[O:12][C:13]([CH3:16])([CH3:15])[CH3:14].[C:18]([C:20]1[C:21](OS(C(F)(F)F)(=O)=O)=[C:22]([C:30]([O:32][CH3:33])=[O:31])[C:23]2[C:28]([CH:29]=1)=[CH:27][CH:26]=[CH:25][CH:24]=2)#[N:19].CC1C=CC(P(C2C=CC3C(=CC=CC=3)C=2C2C3C(=CC=CC=3)C=CC=2P(C2C=CC(C)=CC=2)C2C=CC(C)=CC=2)C2C=CC(C)=CC=2)=CC=1>C1(C)C=CC=CC=1.CCOCC.C(Cl)Cl.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[C:13]([O:12][C:11]([NH:10][CH2:9][CH2:8][S:7][C:21]1[C:20]([C:18]#[N:19])=[CH:29][C:28]2[C:23](=[CH:24][CH:25]=[CH:26][CH:27]=2)[C:22]=1[C:30]([O:32][CH3:33])=[O:31])=[O:17])([CH3:14])([CH3:16])[CH3:15]

Participants

9

Reactant 4

HCID 11430Potassium CarbonateHCID 3017761N-(tert-butoxycarbonyl)-2-aminoethanethiolHCID 4189906(S)-(-)-2,2'-Bis(di-p-tolylphosphino)-1, 1'-binaphthylHCID 22593646HCID 22593646, compound2×

Product 1

HCID 22593643HCID 22593643, compoundYield 69.3%

Reagents, catalysts & solvents 4

HCID 167845palladium(II) acetateCatalystHCID 1140TolueneSolvent2×HCID 3283Diethyl EtherSolventHCID 6344DichloromethaneSolvent

Procedure

To a suspension (vacuum degassed 3 times) of potassium carbonate (110 mg, 0.78 mmol) in toluene (5 mL) under nitrogen was added tert-butyl 2-mercaptoethylcarbamate (131 μL, 0.78 mmol) followed by stirring at ambient temperature for 1 h. To this suspension was added by cannula a solution (vacuum degassed 3 times) of methyl 3-cyano-2-{[(trifluoromethyl)-sulfonyl]oxy}-1-naphthoate (Intermediate 1, 200 mg, 0.56 mmol), (R)-Tol-BINAP (44.1 mg, 0.07 mmol), and palladium(II) acetate (14 mg, 0.06 mmol) in toluene (10 mL). The resulting suspension was stirred at 80° C. for 20 h, cooled, (reduced volume by ½ under reduced pressure, diluted with ether (12 ml) and methylene chloride (6 ml), washed organic layer with 20% K2CO3 (2×15 ml), water and brine, dried over Na2SO4, filtered, and evaporated to dryness. The residue was precipitated from 10% ethyl acetate in hexanes to give 150 mg of the title compound. An additional 40 mg (88% overall yield) of the title compound was isolated from the mother liquor by chromatography on silica gel in 20% ethyl acetate/hexanes.

Workup

  1. stirringThe resulting suspension was stirred at 80° C. for 20 h
  2. temperaturecooled
  3. washwashed organic layer with 20% K2CO3 (2×15 ml), water and brine
  4. dry with materialdried over Na2SO4
  5. filtrationfiltered
  6. customevaporated to dryness
  7. customThe residue was precipitated from 10% ethyl acetate in hexanes

Sources & evidence

ORD record
ord-c51471c672da4af0aff8ad7f651329c6
Source dataset
uspto-grants-2007_06
Patent number
US07235541B2

Reaction notes

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