Methyl iodide → HCID 86594393, compound

HRID 2428060Notes

Reaction equation

HRID 2428060 reaction equation
[CH3:1][Si]([N-][Si](C)(C)C)(C)C.[Na+].[CH2:11]([C@@H:18]1[CH2:22][O:21][C:20](=[O:23])[N:19]1[C:24](=[O:88])[CH2:25][CH2:26][C@@H:27]([CH3:87])[C@@H:28]([O:77][CH2:78][C:79]1[CH:84]=[CH:83][C:82]([O:85][CH3:86])=[CH:81][CH:80]=1)[C@@H:29]([CH3:76])[CH:30]=[CH:31][C@@H:32]([O:68][Si:69]([C:72]([CH3:75])([CH3:74])[CH3:73])([CH3:71])[CH3:70])[CH2:33][C@H:34]([O:60][Si:61]([C:64]([CH3:67])([CH3:66])[CH3:65])([CH3:63])[CH3:62])[C@@H:35]([CH3:59])[CH:36]=[CH:37][CH2:38][O:39][C:40]([C:53]1[CH:58]=[CH:57][CH:56]=[CH:55][CH:54]=1)([C:47]1[CH:52]=[CH:51][CH:50]=[CH:49][CH:48]=1)[C:41]1[CH:46]=[CH:45][CH:44]=[CH:43][CH:42]=1)[C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1.CI>C1COCC1>[CH2:11]([C@@H:18]1[CH2:22][O:21][C:20](=[O:23])[N:19]1[C:24](=[O:88])[C@@H:25]([CH3:1])[CH2:26][C@H:27]([CH3:87])[C@@H:28]([O:77][CH2:78][C:79]1[CH:84]=[CH:83][C:82]([O:85][CH3:86])=[CH:81][CH:80]=1)[C@@H:29]([CH3:76])[CH:30]=[CH:31][C@@H:32]([O:68][Si:69]([C:72]([CH3:73])([CH3:74])[CH3:75])([CH3:70])[CH3:71])[CH2:33][C@H:34]([O:60][Si:61]([C:64]([CH3:65])([CH3:66])[CH3:67])([CH3:63])[CH3:62])[C@H:35]([CH3:59])[CH:36]=[CH:37][CH2:38][O:39][C:40]([C:47]1[CH:48]=[CH:49][CH:50]=[CH:51][CH:52]=1)([C:53]1[CH:58]=[CH:57][CH:56]=[CH:55][CH:54]=1)[C:41]1[CH:42]=[CH:43][CH:44]=[CH:45][CH:46]=1)[C:12]1[CH:13]=[CH:14][CH:15]=[CH:16][CH:17]=1

Participants

5

Reactant 3

HCID 6328Methyl iodideHCID 2724254Sodium bis(trimethylsilyl)amideHCID 86594394HCID 86594394, compound

Product 1

HCID 86594393HCID 86594393, compoundYield 62%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

NaHMDS (1.0 M in THF, 1.68 ml) was added at −78° C. to a solution of 68 (1.67 g) in THF (4 ml). After 30 min, the reaction mixture was treated with MeI (0.29 ml) at −78° C., stirred for an additional 4 h, quenched with sat'd aqueous NH4Cl, and extracted with ether (2×10 ml). The combined organic layers were dried (MgSO4), concentrated and purified by flash column chromatography (EtOAc/hexane 1:9) to give product 69 (1.05 g, 62%) as a colorless oil: IR (CHCl3) 2957, 2929, 2856, 1783, 1697, 1513, 1449, 1385, 1249, 1074, 836, 774, 705 cm−1; 1H NMR (300 MHz, CDCl3) δ 7.49 (m, 6H), 7.29 (m, 16H), 6.80 (m, 2H), 5.79 (dd, J=15.6, 6.2 Hz, 1H), 5.56 (dt, J=15.6, 5.7 Hz, 1H), 5.42 (m, 2H), 4.62 (m, 2H), 4.56 (d, J=11.3 Hz, 1H), 4.37 (d, J=11.1 Hz, 1H), 4.17 (m, 1H), 4.05 (m, 1H), 3.92 (m, 1H), 3.77 (s, 3H), 3.58 (d, J=5.2 Hz, 1H), 3.27 (m, 1H), 3.08 (dd, J=6.3, 2.5 Hz, 1H), 2.77 (m, 2H), 2.38 (m, 1H), 1.76 (m, 1H), 1.64 (m, 2H), 1.46 (m, 4H), 1.10 (d, J=6.7 Hz, 3H), 1.00 (d, J=6.3 Hz, 3H), 0.98 (d, J=6.7 Hz, 3H), 0.93 (m, 21H), 0.14 (s, 3H), 0.11 (s, 6H), 0.10 (s, 3H); 13C NMR (75 MHz, CDCl3) δ 177.3, 158.7, 152.8, 144.4, 135.3, 134.9, 133.6, 132.3, 131.3, 129.4, 128.9, 128.8, 128.6, 127.6, 127.2, 126.7, 126.3, 113.5, 86.6, 86.5, 74.0, 72.8, 66.5, 65.8, 65.2, 43.0, 42.5, 37.8, 35.4, 35.3, 33.0, 26.3, 26.0, 25.9, 18.3, 18.1, 17.4, 14.5, 14.2, −2.9, −4.0, −4.1, −4.2; HRMS (ESI) calcd for C68H93NO8Si2K 1146.6077 (M+K)+, found 1146.6079; [α]20D+16.70 (c 1.1, CHCl3).

Workup

  1. customquenched with sat'd aqueous NH4Cl
  2. extractionextracted with ether (2×10 ml)
  3. dry with materialThe combined organic layers were dried (MgSO4)
  4. concentrationconcentrated
  5. custompurified by flash column chromatography (EtOAc/hexane 1:9)

Sources & evidence

ORD record
ord-82cfadc006af4f88b735ebf210d7b72b
Source dataset
uspto-grants-2011_06
Patent number
US07968736B2

Reaction notes

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