Sodium Carbonate → HCID 58994510, compound

HRID 1190228Notes

Reaction equation

HRID 1190228 reaction equation
Br[C:2]1[CH:7]=[C:6]([CH2:8][N:9]2[CH2:14][CH2:13][N:12]([CH2:15][CH2:16][O:17][Si:18]([C:21]([CH3:24])([CH3:23])[CH3:22])([CH3:20])[CH3:19])[CH2:11][CH2:10]2)[CH:5]=[CH:4][C:3]=1[NH2:25].[Li+].[Cl-].[CH3:28][C:29]1([CH3:44])[CH2:34][CH2:33][C:32](B2OC(C)(C)C(C)(C)O2)=[CH:31][CH2:30]1.C([O-])([O-])=O.[Na+].[Na+]>COCCOC.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:21]([Si:18]([CH3:20])([CH3:19])[O:17][CH2:16][CH2:15][N:12]1[CH2:13][CH2:14][N:9]([CH2:8][C:6]2[CH:5]=[CH:4][C:3]([NH2:25])=[C:2]([C:32]3[CH2:33][CH2:34][C:29]([CH3:44])([CH3:28])[CH2:30][CH:31]=3)[CH:7]=2)[CH2:10][CH2:11]1)([CH3:24])([CH3:23])[CH3:22]

Participants

7

Reactant 4

HCID 10340Sodium CarbonateHCID 433294Lithium ChlorideHCID 231420132-(4,4-Dimethylcyclohex-1-en-1-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolaneHCID 58994541HCID 58994541, compound

Product 1

HCID 58994510HCID 58994510, compoundYield 72%

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 80711,2-DimethoxyethaneSolvent

Conditions

Temperature
80 °C

Procedure

A solution of 2-bromo-4-{4-[2-(tert-butyl-dimethyl-silanyloxy)-ethyl]-piperazin-1-ylmethyl}-phenylamine (as prepared in the previous step, 305 mg, 0.712 mmol) in DME (15 mL) was treated with LiCl (36.2 mg, 0.854 mmol), 4,4-dimethyl-cyclohex-1-enyl-4,4,5,5-tetramethyl-[1,3,2]dioxaborolane (202 mg, 8.54 mmol), and aqueous Na2CO3 (2.85 mL, 5.69 mmol, 2.0 M). The mixture was degassed via sonication, placed under Ar, treated with Pd(PPh3)4 (82.2 mg, 0.0712 mmol), and heated to 80° C. for 21 h. The mixture was concentrated in vacuo, and the residue was partitioned between EtOAc (60 mL) and water (60 mL). The layers were separated, and the organic layer was washed with brine (1×20 mL). The combined aqueous layers were extracted with EtOAc (2×20 mL). The combined organic layers were dried over MgSO4 and concentrated in vacuo. Purification of the residue on a 20-g Isolute SPE column on a FlashMaster system with 50% EtOAc-hexane afforded the title compound (233 mg, 72%) as a light tan glassy solid. Mass spectrum (ESI, m/z): Calcd. for C27H47N3OSi, 458.4 (M+H). found 458.1.

Workup

  1. customThe mixture was degassed via sonication
  2. concentrationThe mixture was concentrated in vacuo
  3. customthe residue was partitioned between EtOAc (60 mL) and water (60 mL)
  4. customThe layers were separated
  5. washthe organic layer was washed with brine (1×20 mL)
  6. extractionThe combined aqueous layers were extracted with EtOAc (2×20 mL)
  7. dry with materialThe combined organic layers were dried over MgSO4
  8. concentrationconcentrated in vacuo
  9. customPurification of the residue on a 20-g Isolute SPE column on a FlashMaster system with 50% EtOAc-hexane

Sources & evidence

ORD record
ord-7ae9444ce14547679cc4dd9599b9e3f0
Source dataset
uspto-grants-2014_03
Patent number
US08674100B2

Reaction notes

Loading…