Trifluoromethanesulfonic acid → HCID 87366190, compound

HRID 1670047Notes

Reaction equation

HRID 1670047 reaction equation
[C:1]([O:9][CH:10]([CH2:13][O:14][C@H:15]1[O:44][C@H:43]([CH2:45][O:46][CH2:47][C:48]2[CH:53]=[CH:52][CH:51]=[CH:50][CH:49]=2)[C@@H:34]([O:35][CH2:36][C:37]2[CH:42]=[CH:41][CH:40]=[CH:39][CH:38]=2)[C@H:25]([O:26][CH2:27][C:28]2[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=2)[C@@H:16]1[O:17][CH2:18][C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1)[CH2:11][OH:12])(=[O:8])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.P([O-])([O-])[O-].IN1[C:63](=[O:64])[CH2:62][CH2:61][C:60]1=[O:65].FC(F)(F)S(O)(=O)=O>CCOCC>[C:1]([O:9][CH:10]([CH2:11][O:12][C@H:60]1[O:65][C@H:11]([CH2:10][O:9][CH2:1][C:2]2[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=2)[C@@H:63]([O:64][CH2:36][C:37]2[CH:38]=[CH:39][CH:40]=[CH:41][CH:42]=2)[C@H:62]([O:17][CH2:18][C:19]2[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=2)[C@@H:61]1[O:26][CH2:27][C:28]1[CH:29]=[CH:30][CH:31]=[CH:32][CH:33]=1)[CH2:13][O:14][C@H:15]1[O:44][C@H:43]([CH2:45][O:46][CH2:47][C:48]2[CH:49]=[CH:50][CH:51]=[CH:52][CH:53]=2)[C@@H:34]([O:35][CH2:36][C:37]2[CH:38]=[CH:39][CH:40]=[CH:41][CH:42]=2)[C@H:25]([O:26][CH2:27][C:28]2[CH:29]=[CH:30][CH:31]=[CH:32][CH:33]=2)[C@@H:16]1[O:17][CH2:18][C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1)(=[O:8])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

6

Reactant 4

HCID 62406Trifluoromethanesulfonic acidHCID 107908PhosphiteHCID 120273N-IodosuccinimideHCID 67351808HCID 67351808, compound

Product 1

HCID 87366190HCID 87366190, compoundYield 142.1%

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent2×

Procedure

Powdered 4 Å molecular sieves (50 mg) were added to a solution of glycerol 9 (730 mg, 1.02 mmol), phosphite 10 (771 mg, 1.22 mmol) and N-iodosuccinimide (NIS) (275 mg, 1.22 mmol) in dry ether (20 mL) under an atmosphere of nitrogen. The reaction was stirred at room temperature for 15 minutes, trifluoromethanesulfonic acid (110 μL, 1.24 mmol) was added and the stirring was continued for 2 h. The reaction was diluted with more ether (50 mL) and the organic layer was washed with 10% sodium thiosulfate solution (30 mL), water (2×20 mL) and dried over magnesium sulfate. The solvent was removed and the residue was purified over silica [hexane/ether 9:1 as eluent] to give 11 (900 mg, 71%, α to β 4:1) as a colourless syrup; Rf 0.6 (hexane/ether, 2:3); νmaxcm−1/(CHCl3) 1716.7; 1H NMR (500 MHz, CDCl3) δ inter alia 8.00 (d, J 7.7, 2H), 7.55 (t, J 7.7 Hz, 1H), 7.38-7.08 (m, 40H, Ar—H), 5.53-5.41 and 5.38-4.43 (m, together 1H, H-2′), 4.96 (d, 1H, J 2 Hz, H-1), 4.91 (d, 1H, J 2 Hz, H-1), 4.86 (d, 2H, J 11 Hz, PhCH2), 4.82 (d, 2H, J 11 Hz, PhCH2), 4.72 (d, 2H, J 12.5 Hz, PhCH2), 4.69 (d, 2H, J 12.5 Hz, PhCH2), 4.65-4.55 (m, 4H), 4.52-4.42 (m, 4H), 4.13-3.50 (m, 16H); 13C NMR (125 MHz, CDCl3) 8 inter alia 165.9 (CO), 138.6, 138.5, 138.5, 138.43, 138.42, 138.35 (ipso-C), 133.2 (Cq-benzoyl), 130.0, 129.8, 128.5, 128.41, 128.35, 128.33, 128.29, 128.03, 127.92, 127.87, 127.81, 127.78, 127.76, 127.73, 127.63, 127.60, 127.52, 98.4 and 97.7 (2×C-1), 80.0, 79.9, 75.1, 75.0, 74.9, 74.8, 74.7, 73.42, 73.38, 72.68, 72.65, 72.4, 72.3, 72.2, 71.4, 69.2, 69.1, 65.9, 65.5; LRMS-ESI (+ve) m/z (%) 1265 [MNa+1]+ (18), 1264 (MNa+,47), 91 (100); HRMS-ESI (+ve) (Found: m/z 1241.5595 (MH+). C78H81O14 requires m/z 1241.5626).

Workup

  1. waitthe stirring was continued for 2 h
  2. washthe organic layer was washed with 10% sodium thiosulfate solution (30 mL), water (2×20 mL)
  3. dry with materialdried over magnesium sulfate
  4. customThe solvent was removed
  5. customthe residue was purified over silica [hexane/ether 9:1 as eluent]

Sources & evidence

ORD record
ord-2124649b05a84065acd7f619a92ae55d
Source dataset
uspto-grants-2011_08
Patent number
US07989602B2

Reaction notes

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