Cesium carbonate → HCID 123896102, compound

HRID 628398Notes

Reaction equation

HRID 628398 reaction equation
[Si:1]([O:18][CH2:19][C:20]1[CH:21]=[C:22]([CH:39]=[C:40]([Cl:42])[CH:41]=1)[CH2:23][N:24]1[C:32]2[C:27](=[N:28][C:29](Cl)=[CH:30][CH:31]=2)[CH:26]=[C:25]1[C:34]1[O:35][CH:36]=[N:37][N:38]=1)([C:14]([CH3:17])([CH3:16])[CH3:15])([C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[NH:43]([C:52]([O:54][C:55]([CH3:58])([CH3:57])[CH3:56])=[O:53])[NH:44][C:45]([O:47][C:48]([CH3:51])([CH3:50])[CH3:49])=[O:46].C([O-])([O-])=O.[Cs+].[Cs+]>C1(C)C=CC=CC=1.O.C1(P(C2CCCCC2)C2C=CC=CC=2C2C(C(C)C)=CC(C(C)C)=CC=2C(C)C)CCCCC1.NC1C=CC=CC=1C1C=CC=CC=1[Pd]Cl>[Si:1]([O:18][CH2:19][C:20]1[CH:21]=[C:22]([CH:39]=[C:40]([Cl:42])[CH:41]=1)[CH2:23][N:24]1[C:32]2[C:27](=[N:28][C:29]([N:43]([C:52]([O:54][C:55]([CH3:58])([CH3:57])[CH3:56])=[O:53])[NH:44][C:45]([O:47][C:48]([CH3:49])([CH3:50])[CH3:51])=[O:46])=[CH:30][CH:31]=2)[CH:26]=[C:25]1[C:34]1[O:35][CH:36]=[N:37][N:38]=1)([C:14]([CH3:15])([CH3:16])[CH3:17])([C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1)[C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1

Participants

7

Reactant 3

HCID 10796Cesium carbonate2×HCID 85431Di-tert-butyl bicarbamate2×HCID 123492805HCID 123492805, compound

Product 1

HCID 123896102HCID 123896102, compound

Reagents, catalysts & solvents 3

HCID 178439015HCID 178439015, compoundCatalyst2×HCID 962WaterSolventHCID 1140TolueneSolvent

Conditions

Temperature
110 °C

Procedure

A degassed mixture of 1-[3-({[tert-butyl(diphenyl)silyl]oxy}methyl)-5-chlorobenzyl]-5-chloro-2-(1,3,4-oxadiazol-2-yl)-1H-pyrrolo[3,2-b]pyridine (0.500 g, 0.815 mmol, from Step 2), di-tert-butyl hydrazine-1,2-dicarboxylate (0.21 g, 0.90 mmol, Aldrich), dicyclohexyl(2′,4′,6′-triisopropylbiphenyl-2-yl)phosphine-(2′-aminobiphenyl-2-yl)(chloro)palladium (1:1) (0.076 g, 0.096 mmol, Aldrich) and Cs2CO3 (0.29 g, 0.90 mmol) in toluene (7 mL) was heated at 110° C. for 4 h. Additional di-tert-butyl hydrazine-1,2-dicarboxylate (0.1 g, 0.43 mmol), Cs2CO3 (0.15 g, 0.46 mmol), and dicyclohexyl(2′,4′,6′-triisopropylbiphenyl-2-yl)phosphine-(2′-aminobiphenyl-2-yl)(chloro)palladium (1:1) (0.050 g, 0.063 mmol) were added and heating was continued for 5 h. Upon cooling, the reaction mixture was diluted with water and extracted with three portions of EtOAc. The combined organic extracts were dried over sodium sulfate, filtered and concentrated. Flash chromatography, eluting with a gradient from 0-50% EtOAc in hexanes was used to purify product. Yield: (0.26 g, 39%).

Workup

  1. temperatureheating
  2. temperatureUpon cooling
  3. extractionextracted with three portions of EtOAc
  4. dry with materialThe combined organic extracts were dried over sodium sulfate
  5. filtrationfiltered
  6. concentrationconcentrated
  7. washFlash chromatography, eluting with a gradient from 0-50% EtOAc in hexanes
  8. customto purify product

Sources & evidence

ORD record
ord-c96dc66a71674ee09e698e1c6eba64bc
Source dataset
uspto-grants-2016_04
Patent number
US09309246B2

Reaction notes

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