tert-Butanol → trans-Methyl 2-(dibenzylamino)cycloheptanecarboxylate

HRID 1011536Notes

Reaction equation

HRID 1011536 reaction equation
C[Si]([N-][Si](C)(C)C)(C)C.[K+].C(O)(C)(C)C.[CH2:16]([N:23]([CH2:35][C:36]1[CH:41]=[CH:40][CH:39]=[CH:38][CH:37]=1)[C@H:24]1[CH2:30][CH2:29][CH2:28][CH2:27][CH2:26][C@H:25]1[C:31]([O:33][CH3:34])=[O:32])[C:17]1[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=1>O1CCCC1>[CH2:35]([N:23]([CH2:16][C:17]1[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=1)[C@@H:24]1[CH2:30][CH2:29][CH2:28][CH2:27][CH2:26][C@H:25]1[C:31]([O:33][CH3:34])=[O:32])[C:36]1[CH:37]=[CH:38][CH:39]=[CH:40][CH:41]=1

Participants

5

Reactant 3

HCID 6386tert-ButanolHCID 3251421Potassium bis(trimethylsilyl)amideHCID 67315403cis-Methyl 2-(dibenzylamino)cycloheptanecarboxylate

Product 1

HCID 59497788trans-Methyl 2-(dibenzylamino)cycloheptanecarboxylateYield 67.4%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

Potassium bis(trimethylsilyl)amide (31.7 mL, 15.9 mmol) was added dropwise to a solution of t-butanol in anhydrous tetrahydrofuran under nitrogen at room temperature. After 30 min, a solution of cis-methyl 2-(dibenzylamino)cycloheptanecarboxylate (1.33 g, 3.78 mmol) in 50 mL anhydrous tetrahydrofuran was added dropwise via syringe. The reaction was stirred for 17 h and then was partitioned between 250 mL diethyl ether and 200 mL brine. The organic layer was concentrated and purified by flash chromatography on 120 g silica gel with 2 to 4% ethyl acetate in hexane to yield trans-methyl 2-(dibenzylamino)cycloheptanecarboxylate (895 mg, 67%). 1H NMR (400 MHz, CDCl3) δ ppm 7.23-7.30 (8H, m), 7.16-7.22 (2H, m), 3.77 (2H, d, J=13.60 Hz), 3.51 (3H, s), 3.26 (2H, d, J=13.35 Hz), 3.02 (1H, ddd, J=11.08, 8.81, 2.77 Hz), 2.77 (1H, ddd, J=11.02, 6.99, 4.41 Hz), 1.88-1.99 (1H, m), 1.28-1.83 (9H, m).

Workup

  1. customwas partitioned between 250 mL diethyl ether and 200 mL brine
  2. concentrationThe organic layer was concentrated
  3. custompurified by flash chromatography on 120 g silica gel with 2 to 4% ethyl acetate in hexane

Sources & evidence

ORD record
ord-a5f026a4c36746e9a237ae0fefb527e7
Source dataset
uspto-grants-2011_07
Patent number
US07977362B2

Reaction notes

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