Diisopropylamine → HCID 18957380, compound

HRID 2379546Notes

Reaction equation

HRID 2379546 reaction equation
[CH3:1][C:2]([Si:5]([CH3:19])([CH3:18])[O:6][C:7]1[CH:8]=[C:9]([CH2:13][C:14]([O:16][CH3:17])=[O:15])[CH:10]=[CH:11][CH:12]=1)([CH3:4])[CH3:3].[Li+].CC([N-]C(C)C)C.[Li]CCCC.N(C(C)C)C(C)C.Br[CH2:41][C:42]1[O:43][C:44]([C:53]2[CH:58]=[CH:57][CH:56]=[CH:55][CH:54]=2)=[C:45]([C:47]2[CH:52]=[CH:51][CH:50]=[CH:49][CH:48]=2)[N:46]=1.[NH4+].[Cl-]>C1COCC1>[CH3:4][C:2]([Si:5]([CH3:18])([CH3:19])[O:6][C:7]1[CH:8]=[C:9]([CH:13]([CH2:41][C:42]2[O:43][C:44]([C:53]3[CH:58]=[CH:57][CH:56]=[CH:55][CH:54]=3)=[C:45]([C:47]3[CH:52]=[CH:51][CH:50]=[CH:49][CH:48]=3)[N:46]=2)[C:14]([O:16][CH3:17])=[O:15])[CH:10]=[CH:11][CH:12]=1)([CH3:1])[CH3:3]

Participants

8

Reactant 6

HCID 7912DiisopropylamineHCID 25517Ammonium ChlorideHCID 5685992-Bromomethyl-4,5-diphenyl-oxazoleHCID 2724682Lithium diisopropylamideHCID 18957372HCID 18957372, compoundHCID 178418339Butyllithium

Product 1

HCID 18957380HCID 18957380, compoundYield 56.1%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent3×

Conditions

Temperature
-78 °C

Procedure

A solution of methyl 3-[[(1,1-dimethylethyl)dimethylsilyl]oxy]benzeneacetate (12.00 g, 43 mmol) in dry THF (40 mL) was added dropwise to a solution of LDA (prepared from nBuLi (20.70 mL of a 2.5 M solution, 3.32 g, 51 mmol) and iPr2NH (4.79 g, 6.60 mL, 47 mmol)) in THF (300 mL) maintained at about -78° C. under an atmosphere of N2. After about 15 minutes, 2-bromomethyl-4,5-diphenyloxazole (14.86 g, 47 mmol) in THF (20 mL) was added dropwise. The mixture was stirred for about 30 minutes at about -78° C., poured onto saturated NH4Cl solution and extracted with CH2Cl2. The combined extracts were dried over Na2SO4, concentrated and the residual oil chromatographed on a column of silica gel. Elution with a mixture of hexanes and Et2O (9:1) gave methyl α -[3-[[(1,1-dimethylethyl)dimethylsilyl]oxy]phenyl]-4,5-diphenyl-2-oxazolepropanoate (12.40 g, 56%) 1H NMR (CDCl3) δ0.18 (6H, s, Si(CH3)2), 0.98 (9H, s, (CH3)3C), 3.23 and 3.65 (2H, d of ABq, J=16 Hz, J'=8 Hz, CH2 -oxazole), 3.72 (3H, s, CO2CHH3), 4.29 (1H, dd, J=8 Hz, CHCO2CH3), 6.77 (1H, d, J=9 Hz, aromatic H), 6.88 (1H, s, aromatic H), 6.98 (1H, d, J=9 Hz, aromatic H), 7.20 (1H, t, J=8Hz, aromatic H), 7.25 to 7.45 (6H, m, aromatic H), 7.45 to 7.70 (4H, m, aromatic H).

Workup

  1. extractionextracted with CH2Cl2
  2. dry with materialThe combined extracts were dried over Na2SO4
  3. concentrationconcentrated
  4. customthe residual oil chromatographed on a column of silica gel
  5. washElution
  6. additionwith a mixture of hexanes and Et2O (9:1)

Sources & evidence

ORD record
ord-14f1d18377b847ff8d56743380e94682
Source dataset
uspto-grants-1994_11
Patent number
US05362879

Reaction notes

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