Methyl iodide → HCID 68853379, compound

HRID 2252480Notes

Reaction equation

HRID 2252480 reaction equation
[CH3:1][Si]([N-][Si](C)(C)C)(C)C.[Na+].[CH3:11][O:12][C:13]1[CH:51]=[CH:50][C:16]([CH2:17][O:18][CH2:19][C@H:20]([CH3:49])[C@H:21]([O:41][Si:42]([C:45]([CH3:48])([CH3:47])[CH3:46])([CH3:44])[CH3:43])[C@@H:22]([CH3:40])[CH2:23][CH2:24][C:25]([N:27]2[C@H:31]([CH2:32][C:33]3[CH:38]=[CH:37][CH:36]=[CH:35][CH:34]=3)[CH2:30][O:29][C:28]2=[O:39])=[O:26])=[CH:15][CH:14]=1.CI>C1COCC1>[CH3:11][O:12][C:13]1[CH:51]=[CH:50][C:16]([CH2:17][O:18][CH2:19][C@H:20]([CH3:49])[C@H:21]([O:41][Si:42]([C:45]([CH3:46])([CH3:48])[CH3:47])([CH3:44])[CH3:43])[C@@H:22]([CH3:40])[CH2:23][C@@H:24]([CH3:1])[C:25]([N:27]2[C@H:31]([CH2:32][C:33]3[CH:34]=[CH:35][CH:36]=[CH:37][CH:38]=3)[CH2:30][O:29][C:28]2=[O:39])=[O:26])=[CH:15][CH:14]=1

Participants

5

Reactant 3

HCID 6328Methyl iodideHCID 2724254Sodium bis(trimethylsilyl)amideHCID 68970239HCID 68970239, compound

Product 1

HCID 68853379HCID 68853379, compoundYield 74%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
25 °C

Procedure

NaHMDS (1 M in THF, 14.9 mL, 14.9 mmol) was added dropwise over a 30 min period to a cooled (−78° C.) suspension of the imide 25 (7.91 g, 13.6 mmol) in THF (45 mL). After 15 min of stirring, the resulting cold solution was treated with MeI (2.53 mL, 40.8 mmol) and allowed to stir at −78° C. for 3 h before being warmed to 25° C. overnight (12 h) The reaction was quenched with H2O (100 mL), and the aqueous layer was extracted with Et2O (3×150 mL). The combined organic extracts were dried (MgSO4), concentrated in vacuo and chromatographed (EtOAc/hexane 1:9) to provide 5.97 g (74%) of 26 as a colorless oil: 1H NMR (300 MHz, CDCl3) δ 7.42-7.26 (m, 7H), 6.95-6.92 (m, 2H), 4.71 (m, 1H), 4.51 (m, 2H), 4.18 (m, 2H), 3.95 (m, 1H), 3.84 (s, 3H), 3.63 (dd, J=8.9, 3.8 Hz, 1H), 3.57 (dd, J=6.4, 2.7 Hz, 1H), 3.35 (t, J=8.5 Hz, 1H), 3.28 (dd, J=13.3, 3.1 Hz, 1H), 2.83 (dd, J=13.3, 9.4 Hz, 1H), 2.10-1.95 (m, 2H), 1.68 (m, 1H), 1.38 (ddd, J=14.1, 9.8, 4.9 Hz, 1H), 1.31 (d, J=6.8 Hz, 3H), 1.04 (d, J=6.9 Hz, 3H), 0.98 (s, 9H), 0.95 (d, J=6.7 Hz, 3H), 0.14 (s, 3H), 0.13 (s, 3H); 13C NMR (75 MHz, CDCl3) δ 176.8, 158.8, 152.8, 135.1, 130.8, 129.3, 128.9, 128.7, 127.1, 113.5, 77.6, 72.6, 72.4, 65.7, 55.0, 38.9, 38.0, 37.6, 35.3, 33.8, 26.0, 18.8, 18.3, 14.9, 13.8, −3.8, −4.2.

Workup

  1. temperaturea cooled
  2. stirringto stir at −78° C. for 3 h
  3. customwas quenched with H2O (100 mL)
  4. extractionthe aqueous layer was extracted with Et2O (3×150 mL)
  5. dry with materialThe combined organic extracts were dried (MgSO4)
  6. concentrationconcentrated in vacuo
  7. customchromatographed (EtOAc/hexane 1:9)

Sources & evidence

ORD record
ord-1a2d2edb1d424deca0804508e7dcbe17
Source dataset
uspto-grants-2008_01
Patent number
US07321046B2

Reaction notes

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