Potassium Carbonate → 4,4'-Bipiperidine, 1-boc protected

HRID 1014265Notes

Reaction equation

HRID 1014265 reaction equation
[NH:1]1[CH2:6][CH2:5][CH:4]([CH:7]2[CH2:12][CH2:11][NH:10][CH2:9][CH2:8]2)[CH2:3][CH2:2]1.[CH3:13][C:14]([O:17][C:18](ON=C(C1C=CC=CC=1)C#N)=[O:19])([CH3:16])[CH3:15].C(=O)([O-])[O-].[K+].[K+]>O1CCCC1.C(Cl)(Cl)Cl>[N:1]1([C:18]([O:17][C:14]([CH3:16])([CH3:15])[CH3:13])=[O:19])[CH2:6][CH2:5][CH:4]([CH:7]2[CH2:12][CH2:11][NH:10][CH2:9][CH2:8]2)[CH2:3][CH2:2]1

Participants

6

Reactant 3

HCID 11430Potassium CarbonateHCID 938652-(tert-Butoxycarbonyloxyimino)-2-phenylacetonitrileHCID 7360504,4'-Bipiperidine

Product 1

HCID 117475994,4'-Bipiperidine, 1-boc protectedYield 45.7%

Reagents, catalysts & solvents 2

HCID 6212ChloroformSolventHCID 8028TetrahydrofuranSolvent2×

Procedure

To 4,4′-bipiperidine (5.48 g, 32.6 mmol) in tetrahydrofuran (160 mL) and chloroform (160 mL) was added BOC-ON (4.01 g, 16.2 mmol) in tetrahydrofuran (90 mL) dropwise over an 8 hour period. The reaction was then concentrated and purified by chromatograpy on SiO2. The residue was taken up in 1M KHSO4 (250 mL) and washed with diethyl ether (three times). Potassium carbonate (38.0 g, 275 mmol) was added to the aqueous layer which was subsequently extracted with chloroform (three times), dried (MgSO4), and concentrated to provide 1,1-dimethylethyl 4,4′-bipiperidine-1-carboxylate (1.98 g, 7.40 mmol, 45%). 1H NMR (400 MHz, CDCl3) δ ppm 1.06-1.18 (m, 6 H), 1.42 (s, 9 H), 1.58-1.69 (m, 6 H), 2.50-2.61 (m, 4 H), 3.06 (d, J=12.1 Hz, 2 H), 4.08 (br s, 1 H).

Workup

  1. concentrationThe reaction was then concentrated
  2. custompurified by chromatograpy on SiO2
  3. washwashed with diethyl ether (three times)
  4. extractionwas subsequently extracted with chloroform (three times)
  5. dry with materialdried (MgSO4)
  6. concentrationconcentrated

Sources & evidence

ORD record
ord-01081f0ecea64feca1d0613961f5288a
Source dataset
uspto-grants-2011_07
Patent number
US07981903B2

Reaction notes

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