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Potassium Carbonate → tert-butyl 2-[(1R)-5-pyrimidin-2-yl-2,3-dihydro-1H-inden-1-yl]-2,7-diazaspiro[3.5]nonane-7-carboxylate

HRID 1913454
Notes
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Reaction equation

HRID 1913454 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.B1(B2OC(C)(C)C(C)(C)O2)OC(C)(C)C(C)(C)O1.C([O-])(=O)C.[K+].Cl[C:51]1[N:56]=[CH:55][CH:54]=[CH:53][N:52]=1.C([O-])([O-])=O.[K+].[K+]>C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2].O1CCOCC1>[N:52]1[CH:53]=[CH:54][CH:55]=[N:56][C:51]=1[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([CH2:15][CH2:16][N:17]([C:20]([O:22][C:23]([CH3:24])([CH3:26])[CH3:25])=[O:21])[CH2:18][CH2:19]3)[CH2:12]1)[CH2:6][CH2:5]2
ParticipantsConditionsProcedureWorkupSources & evidenceReaction notes

Participants

8

Reactant 5

HCID 11430Potassium CarbonateHCID 744042-ChloropyrimidineHCID 517044Potassium AcetateHCID 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 67411761
tert-butyl 2-[(1R)-5-pyrimidin-2-yl-2,3-dihydro-1H-inden-1-yl]-2,7-diazaspiro[3.5]nonane-7-carboxylate
Yield 78.5%

Reagents, catalysts & solvents 2

HCID 44119782Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)Catalyst2×HCID 312751,4-DioxaneSolvent

Conditions

Temperature
110 °C

Procedure

To an oven-dried round-bottomed flask was added tert-butyl 2-[(1R)-5-bromo-2,3-dihydro-1H-inden-1-yl]-2,7-diazaspiro[3.5]nonane-7-carboxylate (3-1a, 267 mg, 0.63 mmol), anhydrous dioxane (9 mL), bis(pinacolato)diboron (177 mg, 0.69 mmol) and potassium acetate (249 mg, 2.53 mmol). The resulting mixture was purged with nitrogen for 15 minutes. Pd(dppf)Cl2 (15 mg, 0.02 mmol) was added and the reaction mixture was purged with nitrogen for an additional 15 minutes. The reaction was heated under nitrogen at 110° C. for 5 hours. After consumption of the starting material (as monitored by TLC), the reaction was cooled to room temperature and 2-chloro-pyrimidine (71.0 mg, 0.63 mmol), Pd(dppf)Cl2 (15 mg, 0.02 mmol) and aqueous K2CO3 solution (2M, 2.25 mL, de-oxygenated with nitrogen for 15 minutes prior to addition) were added. The reaction was purged with nitrogen (3×) and heated under nitrogen for 20 hours at 110° C. The reaction was cooled to room temperature and was filtered through a short plug of silica gel, eluting with methanol. The solvents were removed in vacuo and the residue was partitioned between 50 mL of ethyl acetate and 50 mL of 1N NaOH solution. The layers were separated and the organic layer was washed with 50 mL of brine. The organic layer was dried (Na2SO4) and concentrated to give the crude product as a black semi-solid. The crude product was purified by column chromatography using a Combiflash ISCO purification system (Teledyne Isco Inc., Lincoln, Nebr.) system, eluting with 0-10% MeOH in CH2Cl2 to give the title compound as a black gum (208 mg, 78%). MS (ES+) 421.2 (M+H)+. 1H NMR (CDCl3) δ 1.39 (s, 9H), 1.59-1.69 (m, 4H), 1.75-1.94 (m, 1H), 2.12 (dq, 1H), 2.76-2.92 (m, 1H), 2.95-3.18 (m, 5H), 3.19-3.36 (m, 4H), 3.92 (dd, 1H), 7.09 (t, 1H), 7.33 (d, 1H), 8.18-8.26 (m, 2H), 8.71 (d, 2H).

Workup

  1. customThe resulting mixture was purged with nitrogen for 15 minutes
  2. customthe reaction mixture was purged with nitrogen for an additional 15 minutes
  3. customAfter consumption of the starting material (as monitored by TLC)
  4. temperaturethe reaction was cooled to room temperature
  5. additionto addition)
  6. additionwere added
  7. customThe reaction was purged with nitrogen (3×)
  8. temperatureheated under nitrogen for 20 hours at 110° C
  9. temperatureThe reaction was cooled to room temperature
  10. filtrationwas filtered through a short plug of silica gel
  11. washeluting with methanol
  12. customThe solvents were removed in vacuo
  13. customthe residue was partitioned between 50 mL of ethyl acetate and 50 mL of 1N NaOH solution
  14. customThe layers were separated
  15. washthe organic layer was washed with 50 mL of brine
  16. dry with materialThe organic layer was dried (Na2SO4)
  17. concentrationconcentrated
  18. customto give the crude product as a black semi-solid
  19. customThe crude product was purified by column chromatography
  20. customa Combiflash ISCO purification system (Teledyne Isco Inc., Lincoln, Nebr.) system
  21. washeluting with 0-10% MeOH in CH2Cl2

Sources & evidence

ORD record
ord-9a6c7101a490496d92324f486e8750eb
Source dataset
uspto-grants-2013_12
DOI
10.6084/m9.figshare.5104873.v1
Patent number
US08609680B2

Reaction notes

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On this pageParticipantsConditionsProcedureWorkupSources & evidenceReaction notes