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Hydrochloric Acid → 2-[(R)-5-(6-Methylpyrimidin-4-yl)-indan-1-yl]-2,7-diazaspiro[3.5]nonane-7-carboxylic acid tert-butyl ester

HRID 2205091
Notes
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Reaction equation

HRID 2205091 reaction equation
Br[C:2]1[CH:3]=[C:4]2[C:8](=[CH:9][CH:10]=1)[C@H:7]([N:11]1[CH2:14][C:13]3([CH2:19][CH2:18][N:17]([C:20]([O:22][C:23]([CH3:26])([CH3:25])[CH3:24])=[O:21])[CH2:16][CH2:15]3)[CH2:12]1)[CH2:6][CH2:5]2.C([O-])(=O)C.[K+].B1(B2OC(C)(C)C(C)(C)O2)OC(C)(C)C(C)(C)O1.[OH-].[Na+].Cl[C:53]1[CH:58]=[C:57]([CH3:59])[N:56]=[CH:55][N:54]=1.Cl>Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.O>[CH3:59][C:57]1[N:56]=[CH:55][N:54]=[C:53]([C:2]2[CH:3]=[C:4]3[C:8](=[CH:9][CH:10]=2)[C@H:7]([N:11]2[CH2:12][C:13]4([CH2:19][CH2:18][N:17]([C:20]([O:22][C:23]([CH3:25])([CH3:24])[CH3:26])=[O:21])[CH2:16][CH2:15]4)[CH2:14]2)[CH2:6][CH2:5]3)[CH:58]=1
ParticipantsConditionsProcedureWorkupSources & evidenceReaction notes

Participants

9

Reactant 6

HCID 313Hydrochloric AcidHCID 14798Sodium HydroxideHCID 517044Potassium AcetateHCID 5817964-Chloro-6-methylpyrimidineHCID 2733548Bis(pinacolato)diboraneHCID 53392276tert-Butyl (R)-2-(5-bromo-2,3-dihydro-1H-inden-1-yl)-2,7-diazaspiro[3.5]nonane-7-carboxylate

Product 1

HCID 674086712-[(R)-5-(6-Methylpyrimidin-4-yl)-indan-1-yl]-2,7-diazaspiro[3.5]nonane-7-carboxylic acid tert-butyl esterYield 86.3%

Reagents, catalysts & solvents 2

HCID 178418476HCID 178418476, compoundCatalystHCID 962WaterSolvent

Conditions

Temperature
100 °C

Procedure

To a 50 mL flask charged with (R)-tert-butyl 2-(5-bromo-2,3-dihydro-1H-inden-1-yl)-2,7-diazaspiro[3.5]nonane-7-carboxylate (4.0 g, 9.49 mmol) was added bis(triphenylphosphine)palladium(II) chloride (0.17 g, 0.24 mmol), potassium acetate (3.73 g, 37.97 mmol), bis(pinacolato)diboron (2.65 g, 10.44 mmol) followed by degassing via vacuum then backfilling with nitrogen 5 times. De-oxygenated (nitrogen stream for 30 minutes prior to addition) toluene (40 mL) was added to the mixture and the reaction was heated at 100° C. for 1.5 hours. The reaction was monitored for completion by HPLC. Upon formation of the boronic ester intermediate, the reaction was cooled to 40° C. and charged with a degassed solution of 4 M sodium hydroxide (11.87 mL, 47.46 mmol) followed by addition of 4-chloro-6-methylpyrimidine (1.53 g, 11.87 mmol). The resulting mixture was then heated to 90° C. for 5 hours under nitrogen. The reaction was cooled to room temperature and charged with water (25 mL). After stirring for 20 minutes, the mixture was filtered to remove black solids. The organic layer was extracted to an aqueous solution containing 1.5 equiv of HCl (40 mL). The organic layer was removed and the resulting solution was treated with (4 g) ISOLUTE® Ultra Pure Si-Thiol silica gel for 1.5 hours and filtered. The aqueous solution was adjusted to pH 7.8 with 4N NaOH and extracted with toluene (40 mL). The toluene layer was concentrated to approximately 15 mL under vacuum at 45° C. and heptane (75 mL) was added slowly and the mixture was stirred at 20° C. for 1 hour. The product was filtered and dried under vacuum at 45° C. for 8 hours to afford the title compound as a white solid (3.56 g, 86%). MS (ES+) 435.5 (M+H)+. 1H NMR (CDCl3) δ 1.46 (s, 9H), 1.70-1.74 (m, 4H), 1.90-2.01 (m, 1H), 2.13-2.26 (m, 1H), 2.59 (s, 3H), 2.84-2.93 (m, 1H), 3.04-3.21 (m, 5H), 3.30-3.38 (m, 4H), 3.95-4.02 (m, 1H), 7.40 (d, 1H), 7.56 (s, 1H), 7.87 (d, 1H), 7.95 (s, 1H), 9.12 (s, 1H).

Workup

  1. customby degassing via vacuum
  2. additionto addition) toluene (40 mL)
  3. additionwas added to the mixture
  4. temperatureUpon formation of the boronic ester intermediate, the reaction was cooled to 40° C.
  5. temperatureThe resulting mixture was then heated to 90° C. for 5 hours under nitrogen
  6. temperatureThe reaction was cooled to room temperature
  7. filtrationthe mixture was filtered
  8. customto remove black solids
  9. extractionThe organic layer was extracted to an aqueous solution
  10. customThe organic layer was removed
  11. additionthe resulting solution was treated with (4 g) ISOLUTE® Ultra Pure Si-Thiol silica gel for 1.5 hours
  12. filtrationfiltered
  13. extractionextracted with toluene (40 mL)
  14. concentrationThe toluene layer was concentrated to approximately 15 mL under vacuum at 45° C.
  15. additionheptane (75 mL) was added slowly
  16. stirringthe mixture was stirred at 20° C. for 1 hour
  17. filtrationThe product was filtered
  18. customdried under vacuum at 45° C. for 8 hours

Sources & evidence

ORD record
ord-7e323fadd6fe43728cd420cd0ec43981
Source dataset
uspto-grants-2016_06
DOI
10.6084/m9.figshare.5104873.v1
Patent number
US09370516B2

Reaction notes

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