Methanol → HCID 12001303, compound

HRID 1012863Notes

Reaction equation

HRID 1012863 reaction equation
C([O:5][C:6](=[O:40])[CH2:7][CH2:8][C@@H:9]1[C:31](=[O:32])[NH:30][C@@H:22]2[CH2:23][S:24][S:25][CH2:26][CH2:27][CH:28]=[CH:29][C@@H:13]([O:14][C:15](=[O:38])[CH2:16][NH:17][C:18](=[O:37])[C@@H:19]([CH:34]([CH3:36])[CH3:35])[NH:20][C:21]2=[O:33])[CH2:12][C:11](=[O:39])[NH:10]1)(C)(C)C.[SiH](CC)(CC)CC.C(O)(C(F)(F)F)=O.CO>C(Cl)Cl>[CH:34]([C@H:19]1[NH:20][C:21](=[O:33])[C@@H:22]2[NH:30][C:31](=[O:32])[C@@H:9]([CH2:8][CH2:7][C:6]([OH:40])=[O:5])[NH:10][C:11](=[O:39])[CH2:12][C@@H:13]([CH:29]=[CH:28][CH2:27][CH2:26][S:25][S:24][CH2:23]2)[O:14][C:15](=[O:38])[CH2:16][NH:17][C:18]1=[O:37])([CH3:36])[CH3:35]

Participants

6

Reactant 4

HCID 887MethanolHCID 6422Trifluoroacetic acidHCID 12052TriethylsilaneHCID 12001302HCID 12001302, compound

Product 1

HCID 12001303HCID 12001303, compound

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

To a solution of 9F (12 mg, 0.02 mmol) and Et3SiH (10 μL, 0.06 mmol) in CH2Cl2 (1.5 mL) was added TFA (150 μL, 2.0 mmol). After 6 h the solvent was removed and the residue purified by column chromatography on silica gel (10% methanol/CH2Cl2 then +1% AcOH) to give 1° F. (5.6 mg, 0.01 mmol, 55%) as a white solid: [α]25D −63.4 (c 0.25, MeOH); 1H-NMR (400 MHz, CD3OD) δ 7.5 (1×NH observed, d, J=7.5 Hz, 1H), 5.81 (dddd, J=16.8, 6.8, 4.8, 2.5 Hz, 1H), 5.75-5.67 (m, 2H), 4.62 (ddd, J=11.0, 8.0, 5.5 Hz 1H), 4.28 (d, J=17.5 Hz, 1H), 4.15 (dd, J=9.0, 6.0 Hz, 1H), 3.78 (d, J=17.5 Hz, 1H), 3.43 (d, J=10.5 Hz, 1H), 3.20-3.10 (m, 2H), 3.07-3.00 (m, 2H), 2.94-2.81 (m, 1H), 2.82 (dd, J=13.2, 2.2 Hz, 1H), 2.73-2.50 (m, 4H), 2.38 (q, J=7.0 Hz, 1H), 2.23-1.99 (m, 2H), 0.98 (d, J=6.5 Hz, 3H), 0.92 (d, J=6.5 Hz, 3H); 13C-NMR (100 MHz, CD3OD) δ 176.5 (C), 174.0 (C), 173.5 (C), 173.0 (C), 171.6 (C), 169.5 (C), 131.4 (CH), 131.3 (CH), 72.1 (CH), 66.0 (CH), 58.5 (CH), 57.0 (CH), 42.7 (CH2), 39.7 (CH2), 39.4 (CH2), 36.8 (CH2), 31.8 (CH2), 31.6 (CH2), 28.2 (CH3), 26.6 (CH2), 20.6 (CH3), 20.5 (CH3); LRMS (ES−) m/z 543 (100%, [M−H]−).

Workup

  1. customAfter 6 h the solvent was removed
  2. customthe residue purified by column chromatography on silica gel (10% methanol/CH2Cl2
  3. custom+1% AcOH) to give 1° F. (5.6 mg, 0.01 mmol, 55%) as a white solid

Sources & evidence

ORD record
ord-24d250c766ff4d0192ab4d03ca7770fa
Source dataset
uspto-grants-2011_07
Patent number
US07977304B2

Reaction notes

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