Ammonium Chloride → Tert-butyl isopropyl(5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)thiazol-2-yl)carbamate

HRID 1811077Notes

Reaction equation

HRID 1811077 reaction equation
Br[C:2]1[S:6][C:5]([N:7]([CH:15]([CH3:17])[CH3:16])[C:8](=[O:14])[O:9][C:10]([CH3:13])([CH3:12])[CH3:11])=[N:4][CH:3]=1.C([Li])CCC.C(O[B:27]1[O:31][C:30]([CH3:33])([CH3:32])[C:29]([CH3:35])([CH3:34])[O:28]1)(C)C.[Cl-].[NH4+]>C1COCC1>[C:10]([O:9][C:8](=[O:14])[N:7]([CH:15]([CH3:17])[CH3:16])[C:5]1[S:6][C:2]([B:27]2[O:31][C:30]([CH3:33])([CH3:32])[C:29]([CH3:35])([CH3:34])[O:28]2)=[CH:3][N:4]=1)([CH3:13])([CH3:12])[CH3:11]

Participants

6

Reactant 4

HCID 25517Ammonium ChlorideHCID 50177412-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolaneHCID 58688351Tert-butyl 5-bromothiazol-2-yl(isopropyl)carbamate2×HCID 178418339Butyllithium

Product 1

HCID 58688452Tert-butyl isopropyl(5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)thiazol-2-yl)carbamateYield 48.6%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-78 °C

Procedure

A solution of tert-butyl 5-bromothiazol-2-yl(isopropyl)carbamate (Intermediate 43-1, 7.5 g, 23.3 mmol) in THF (50 mL) was treated with n-butyllithium (1.6 M in hexane, 21.8 mL, 34.88 mmol) dropwise at −78° C. The resulting solution was stirred at −78° C. for 10 min, then was treated dropwise with 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (6.49 g, 34.9 mmol). The mixture was stirred at −78° C. for 2 h, then was warmed to rt and treated with 50% aqueous ammonium chloride (50 mL). The mixture was extracted with EtOAc (100 mL) and the organic layer was washed with water and brine, and dried and concentrated. The residue was slurried in hexane (30 mL) and the precipitate was collected by filtration, washed with hexane (20 mL) and dried to give tert-butyl-isopropyl(5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)thiazol-2-yl)carbamate as a yellow solid (4.17 g, 48%). 1H NMR (400 MHz, chloroform-d) δ 7.95 (s, 1H) 5.37 (m, 1H) 1.60 (s, 9H) 1.44 (d, 6.7 Hz, 6H) 1.34 (s, 12H).

Workup

  1. stirringThe mixture was stirred at −78° C. for 2 h
  2. temperaturewas warmed to rt
  3. extractionThe mixture was extracted with EtOAc (100 mL)
  4. washthe organic layer was washed with water and brine
  5. customdried
  6. concentrationconcentrated
  7. filtrationthe precipitate was collected by filtration
  8. washwashed with hexane (20 mL)
  9. customdried

Sources & evidence

ORD record
ord-c1e3171b5f2943c38bccc70e210d30f2
Source dataset
uspto-grants-2013_01
Patent number
US08362065B2

Reaction notes

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