Methyl iodide → HCID 66833759, compound

HRID 579555Notes

Reaction equation

HRID 579555 reaction equation
[C:1]([O:5][C:6]([NH:8][CH:9]([CH2:15][CH2:16][CH2:17][CH2:18][B:19]1[O:23][C:22]([CH3:25])([CH3:24])[C:21]([CH3:27])([CH3:26])[O:20]1)[C:10]([O:12][CH2:13][CH3:14])=[O:11])=[O:7])([CH3:4])([CH3:3])[CH3:2].CI.[CH3:30][Si]([N-][Si](C)(C)C)(C)C.[Na+]>C1COCC1>[C:1]([O:5][C:6]([N:8]([CH3:30])[CH:9]([CH2:15][CH2:16][CH2:17][CH2:18][B:19]1[O:20][C:21]([CH3:26])([CH3:27])[C:22]([CH3:25])([CH3:24])[O:23]1)[C:10]([O:12][CH2:13][CH3:14])=[O:11])=[O:7])([CH3:2])([CH3:3])[CH3:4]

Participants

5

Reactant 3

HCID 6328Methyl iodide2×HCID 2724254Sodium bis(trimethylsilyl)amideHCID 66833460HCID 66833460, compound

Product 1

HCID 66833759HCID 66833759, compoundYield 55%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

A solution of ethyl 2-(tert-butoxycarbonylamino)-6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)hexanoate (104 mg, 0.27 mmol) in THF (2.7 mL) was cooled to 0° C. and treated with methyl iodide (0.084 mL, 1.35 mmol) and NaHMDS (0.41 mL, 1 M solution in THF, 0.41 mmol). After stirring for 16 h at room temperature, additional methyl iodide (0.042 mL, 0.77 mmol) was added and the mixture was warmed to 35° C. for 6 hours. The reaction was quenched with saturated NH4Cl solution (2 mL), diluted with ethyl acetate, washed with saturated aqueous sodium bicarbonate solution, sat'd aq sodium chloride, dried over MgSO4 and concentrated. Purification by column chromatography (5-40% ethyl acetate in heptane) gave ethyl 2-(tert-butoxycarbonyl(methyl)amino)-6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)hexanoate (59 mg, 55%). Rf 0.34 (20% ethyl acetate in heptane). 1H NMR (CDCl3, 300 MHz) δ 4.72-4.68, 4.43-4.38 (m, 1H, rotamers), 4.15 (q, J=7.3 Hz, 2H), 2.81, 2.77 (s, 3H, rotamers), 1.87-1.61 (m, 2H), 1.53-1.23 (m, 28H), 0.78 (t, J=7.3 Hz, 2H). ESI MS found for C20H38B1N1O6 m/z [400.5 (M+1)].

Workup

  1. temperaturethe mixture was warmed to 35° C. for 6 hours
  2. customThe reaction was quenched with saturated NH4Cl solution (2 mL)
  3. additiondiluted with ethyl acetate
  4. washwashed with saturated aqueous sodium bicarbonate solution
  5. dry with materialdried over MgSO4
  6. concentrationconcentrated
  7. customPurification by column chromatography (5-40% ethyl acetate in heptane)

Sources & evidence

ORD record
ord-8b83231142dd49fa966ea986daa64cdd
Source dataset
uspto-grants-2015_05
Patent number
US09040703B2

Reaction notes

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