Binap, (A+-)- → HCID 58504049, compound

HRID 2407681Notes

Reaction equation

HRID 2407681 reaction equation
Br[C:2]1[C:10]2[C:5](=[CH:6][CH:7]=[C:8]([C:11]3[N:15]=[CH:14][N:13]([C:16]([C:29]4[CH:34]=[CH:33][CH:32]=[CH:31][CH:30]=4)([C:23]4[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=4)[C:17]4[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=4)[N:12]=3)[CH:9]=2)[N:4]([CH:35]2[CH2:40][CH2:39][CH2:38][CH2:37][O:36]2)[N:3]=1.[C:41]1([C:47]2[CH:51]=[C:50]([CH2:52][N:53]3[CH2:58][CH2:57][CH:56]([CH2:59][NH2:60])[CH2:55][CH2:54]3)[O:49][N:48]=2)[CH:46]=[CH:45][CH:44]=[CH:43][CH:42]=1.C1(P(C2C=CC=CC=2)C2C=CC3C(=CC=CC=3)C=2C2C3C(=CC=CC=3)C=CC=2P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.CC(C)([O-])C.[Na+]>C1(C)C=CC=CC=1>[C:41]1([C:47]2[CH:51]=[C:50]([CH2:52][N:53]3[CH2:54][CH2:55][CH:56]([CH2:59][NH:60][C:2]4[C:10]5[C:5](=[CH:6][CH:7]=[C:8]([C:11]6[N:15]=[CH:14][N:13]([C:16]([C:29]7[CH:34]=[CH:33][CH:32]=[CH:31][CH:30]=7)([C:23]7[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=7)[C:17]7[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=7)[N:12]=6)[CH:9]=5)[N:4]([CH:35]5[CH2:40][CH2:39][CH2:38][CH2:37][O:36]5)[N:3]=4)[CH2:57][CH2:58]3)[O:49][N:48]=2)[CH:42]=[CH:43][CH:44]=[CH:45][CH:46]=1

Participants

6

Reactant 4

HCID 634876Binap, (A+-)-HCID 22479811HCID 22479811, compoundHCID 23676156Sodium t-butoxideHCID 58504252HCID 58504252, compound

Product 1

HCID 58504049HCID 58504049, compound

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Conditions

Temperature
100 °C

Procedure

3-Bromo-1-(tetrahydro-2H-pyran-2-yl)-5-(1-trityl-1H-1,2,4-triazol-3-yl)-1H-indazole (0.25 g, prepared according to the reported preparation in US 2004/0127536), the compound prepared in Example 9 (0.29 g), racemic-2,2′-bis(diphenylphosphino)-1,1′-binaphthyl (0.040 g), and sodium tert-butoxide (0.20 g) were suspended in toluene (6 mL) and purged with argon. Tris(dibenzylideneacetone)dipalladium(0) (0.019 g) was added and the system was sealed and heated at 100° C. overnight. The reaction mixture was cooled to room temperature and partitioned between dichloromethane and a saturated aqueous sodium bicarbonate solution. The organics were dried over anhydrous magnesium sulfate and concentrated. The residue was purified by column chromatography on silica gel to obtain the title compound (0.13 g) having the following physical data.

Workup

  1. custompurged with argon
  2. additionTris(dibenzylideneacetone)dipalladium(0) (0.019 g) was added
  3. customthe system was sealed
  4. temperatureThe reaction mixture was cooled to room temperature
  5. custompartitioned between dichloromethane
  6. dry with materialThe organics were dried over anhydrous magnesium sulfate
  7. concentrationconcentrated
  8. customThe residue was purified by column chromatography on silica gel

Sources & evidence

ORD record
ord-3fa005591d3f45e2b2170897c04c9218
Source dataset
uspto-grants-2014_08
Patent number
US08809538B2

Reaction notes

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