N,N,N',N'-Tetramethylethylenediamine → HCID 10523738, compound

HRID 1019291Notes

Reaction equation

HRID 1019291 reaction equation
[C:1]([O:5][C:6]([NH:8][C:9]1[CH:14]=[CH:13][CH:12]=[C:11]([O:15][CH2:16][O:17][CH3:18])[CH:10]=1)=[O:7])([CH3:4])([CH3:3])[CH3:2].CN(CCN(C)C)C.[Li]CCCC.ClCC[I:35]>C1COCC1.O.[Au]>[C:1]([O:5][C:6]([NH:8][C:9]1[CH:14]=[CH:13][CH:12]=[C:11]([O:15][CH2:16][O:17][CH3:18])[C:10]=1[I:35])=[O:7])([CH3:4])([CH3:3])[CH3:2]

Participants

8

Reactant 4

HCID 8037N,N,N',N'-TetramethylethylenediamineHCID 1364381-Chloro-2-iodoethaneHCID 150893611,1-Dimethylethyl N-[3-(methoxymethoxy)phenyl]carbamateHCID 178418339Butyllithium

Product 1

HCID 10523738HCID 10523738, compound

Reagents, catalysts & solvents 3

HCID 23985GoldCatalystHCID 962WaterSolventHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
25 °C

Procedure

A solution of 13 (124 mg, 0.49 mmol) in 2.0 mL anhydrous THF was cooled to −20° C. and treated with TMEDA (0.26 mL, 1.71 mmol) followed by n-BuLi (0.69 mL of a 2.5 M solution in hexanes, 1.71 mmol) in a slow dropwise manner. The resulting gold solution stirred for 4 h at −20° C. The reaction mixture was treated with 1-chloro-2-iodoethane (0.126 mL, 1.71 mmol) and stirred for 15 min at 25° C. The reaction was diluted with H2O (30 mL), extracted with Et2O (3×20 mL), and the combined organic extracts were washed with saturated aqueous NaCl, dried (Na2SO4) and concentrated under reduced pressure. Flash chromatography (SiO2, 2.5×10 cm, 0-10% EtOAc/hexane gradient) yielded recovered 13 (51.8 mg, 41%) and 14 (85.5 mg, 46%) as a white solid: mp 82-84° C.; 1H NMR (CDCl3, 400 MHz) δ 7.72 (d, J=8.2 Hz, 1H), 7.21 (t, J=6.0 Hz, 1H), 7.01 (br s, 1H), 6.72 (dd, J=1.2, 8.2 Hz, 1H), 5.21 (s, 2H), 3.47 (s, 3H), 1.49 (s, 9H); 13C NMR (CDCl3, 100 MHz) δ 156.0, 152.5, 140.1, 129.5, 113.4, 108.9, 94.8, 82.4, 80.9, 54.4, 28.3; IR (film) νmax 3388, 2977, 1736, 1592, 1515, 1465, 1406, 1252, 1226, 1153, 1005 cm−1; FABHRMS (NBA/CsI) m/z 511.9351 (C13H18INO4+C+ requires 511.9335). Anal. Calcd for C13H18INO4: C, 41.18; H, 4.78; N, 3.69. Found: C, 41.19; H, 5.11; N, 3.79.

Workup

  1. extractionextracted with Et2O (3×20 mL)
  2. washthe combined organic extracts were washed with saturated aqueous NaCl
  3. dry with materialdried (Na2SO4)
  4. concentrationconcentrated under reduced pressure
  5. customFlash chromatography (SiO2, 2.5×10 cm, 0-10% EtOAc/hexane gradient) yielded
  6. customrecovered 13 (51.8 mg, 41%) and 14 (85.5 mg, 46%) as a white solid

Sources & evidence

ORD record
ord-9892ba791f8c4c3e970d3ea693271842
Source dataset
uspto-grants-2002_11
Patent number
US06486326B2

Reaction notes

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