Triacetoxyperiodinane → (3aS,6S,6aS)-(9H-Fluoren-9-yl)methyl 6-(methylthio)-3-oxotetrahydro-2H-furo[3,2-b]pyrrole-4(5H)-carboxylate

HRID 1665877Notes

Reaction equation

HRID 1665877 reaction equation
CC(OI1(OC(C)=O)(OC(C)=O)OC(=O)C2C=CC=CC1=2)=O.[OH:23][C@@H:24]1[C@H:28]2[N:29]([C:34]([O:36][CH2:37][CH:38]3[C:50]4[CH:49]=[CH:48][CH:47]=[CH:46][C:45]=4[C:44]4[C:39]3=[CH:40][CH:41]=[CH:42][CH:43]=4)=[O:35])[CH2:30][C@H:31]([S:32][CH3:33])[C@H:27]2[O:26][CH2:25]1>ClCCl>[CH3:33][S:32][C@H:31]1[CH2:30][N:29]([C:34]([O:36][CH2:37][CH:38]2[C:39]3[CH:40]=[CH:41][CH:42]=[CH:43][C:44]=3[C:45]3[C:50]2=[CH:49][CH:48]=[CH:47][CH:46]=3)=[O:35])[C@@H:28]2[C:24](=[O:23])[CH2:25][O:26][C@H:27]12

Participants

4

Reactant 2

HCID 159087TriacetoxyperiodinaneHCID 67441663HCID 67441663, compound

Product 1

HCID 67441003(3aS,6S,6aS)-(9H-Fluoren-9-yl)methyl 6-(methylthio)-3-oxotetrahydro-2H-furo[3,2-b]pyrrole-4(5H)-carboxylateYield 87%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Procedure

Dess-Martin periodinane (130 mg, 0.65 mmol) was added to a stirred solution of alcohol (55) (278 mg, 0.33 mmol) in dichloromethane (10 mL) under an atmosphere of argon. The mixture was stirred for 1 hour then diluted with dichloromethane (25 mL). The organic phase was washed with a mixture of saturated aqueous sodium bicarbonate and 10% aqueous sodium thiosulphate solution (1:1, 20 mL), then dried (Na2SO4), filtered and reduced in vacuo. Flash chromatography over silica, eluting with diethyl ether:pentane mixtures 60:40 to 65:35 gave ketone (56) (113 mg, 87%) as a white solid. TLC (Rf=0.24, Et2O:pentane 2:1); analytical HPLC two main peaks, Rt=15.71 and 15.91 min.; HPLC-MS 396.1 [M+H]+, 414.1 [M+H2O+Na]+, 813.2 [2M+H]+; [α]D18−137.3° (c=2.33, CHCl3). δH(500 MHz, CDCl3) mixture of rotamers approx. 1:1; 2.15 (1.5H, s, SCH3), 2.19 (1.5H, s, SCH3), 3.30-3.38 (1H, m, CHSMe), 3.68-3.80 (1.5H, m, FmocNCH2), 3.93-4.05 (1.5H, m, 0.5×FmocNCH2 and OCH2C═O), 4.10-4.35 (2.5H, m, OCH2C═O, Fmoc-CH, and 0.5×Fmoc-CH2), 4.40-4.54 (2.5H, m 1.5×Fmoc-CH2 and FmocNCH), 4.74-4.84 (1H, m, OCHCHSCH3), 7.28-7.77 (8H, Fmoc aromatic CH); δC (125 MHz, CDCl3); 14.662 (SCH3), 47.133 (Fmoc-CH), 48.449/48.954 (CHSCH3), 50.539/53.419 (FmocNCH2), 61.005/61.420 (FmocNCH), 67.710/68.437 (Fmoc-CH2), 70.733 (OCH2C═O), 85.174/86.042 (OCHCHSCH3), 119.916, 119.987, 124.917, 124.964, 125.240, 125.448, 127.069, 127.712 and 127.969 (Fmoc aromatic CH), 141.255/141.317, 143.627, 143.778 and 144.264 (Fmoc quaternary), 154.942/155.049 (Fmoc C═O), 207.818/207.973 (ketone C═O).

Workup

  1. washThe organic phase was washed with a mixture of saturated aqueous sodium bicarbonate and 10% aqueous sodium thiosulphate solution (1:1, 20 mL)
  2. dry with materialdried (Na2SO4)
  3. filtrationfiltered
  4. washFlash chromatography over silica, eluting with diethyl ether

Sources & evidence

ORD record
ord-afadb59376664cc6b70723a0a2b362f4
Source dataset
uspto-grants-2011_10
Patent number
US08039641B2

Reaction notes

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