Triethylamine → 12-[4-deoxy-2-O-benzyl-3-methyl-beta-D-allopyranosyl]-2,3,9,10-tetrafluoro-12,13-dihydro-5H-indolo[2,3-a]pyrrolo[3,4-c]carbazole-5,7(6H)-dione

HRID 23869Notes

Reaction equation

HRID 23869 reaction equation
[Si]([O:18][CH2:19][C@H:20]1[O:25][C@@H:24]([N:26]2[C:38]3[C:37]4[NH:39][C:40]5[CH:41]=[C:42]([F:47])[C:43]([F:46])=[CH:44][C:45]=5[C:36]=4[C:35]4[C:48](=[O:52])[NH:49][C:50](=[O:51])[C:34]=4[C:33]=3[C:32]3[C:27]2=[CH:28][C:29]([F:54])=[C:30]([F:53])[CH:31]=3)[C@H:23]([O:55][CH2:56][C:57]2[CH:62]=[CH:61][CH:60]=[CH:59][CH:58]=2)[C@@:22]([CH3:64])([OH:63])[CH2:21]1)(C(C)(C)C)(C1C=CC=CC=1)C1C=CC=CC=1.[Si](OC[C@H]1O[C@@H](N2C3C4NC5C=C(F)C(F)=CC=5C=4C4C(=O)NC(=O)C=4C=3C3C2=CC(F)=C(F)C=3)[C@H](OCC2C=CC=CC=2)[C@](C)(O)C1)(C(C)(C)C)(C1C=CC=CC=1)C1C=CC=CC=1.CCN(CC)CC>CC#N.C(OCC)(=O)C>[CH2:56]([O:55][C@@H:23]1[C@:22]([CH3:64])([OH:63])[CH2:21][C@@H:20]([CH2:19][OH:18])[O:25][C@H:24]1[N:26]1[C:38]2[C:37]3[NH:39][C:40]4[CH:41]=[C:42]([F:47])[C:43]([F:46])=[CH:44][C:45]=4[C:36]=3[C:35]3[C:48](=[O:52])[NH:49][C:50](=[O:51])[C:34]=3[C:33]=2[C:32]2[C:27]1=[CH:28][C:29]([F:54])=[C:30]([F:53])[CH:31]=2)[C:57]1[CH:58]=[CH:59][CH:60]=[CH:61][CH:62]=1

Participants

6

Reactant 3

HCID 8471TriethylamineHCID 2075862412-[4-deoxy-6-O-(tert-butyldiphenylsilyl)-2-O-benzyl-3-methyl-beta-D-allopyranosyl]-2,3,9,10-tetrafluoro-12,13-dihydro-5H-indolo[2,3-a]pyrrolo [3,4-c]carbazole-5,7(6H)-dioneHCID 6996431212-[4-deoxy-6-O-(tert-butyldiphenylsilyl)-2-O-benzyl-3-methyl-beta-D-glucopyranosyl]-2,3,9,10-tetrafluoro-12,13-dihydro-5H-indolo[2,3-a]pyrrolo[3,4-c]carbazole-5,7(6H)-dione

Product 1

HCID 6996530712-[4-deoxy-2-O-benzyl-3-methyl-beta-D-allopyranosyl]-2,3,9,10-tetrafluoro-12,13-dihydro-5H-indolo[2,3-a]pyrrolo[3,4-c]carbazole-5,7(6H)-dioneYield 127%

Reagents, catalysts & solvents 2

HCID 6342AcetonitrileSolventHCID 8857Ethyl AcetateSolvent

Procedure

To a solution of this material ( ) in 5 mL of dry THF, at −78° C. under Ar, was added MeMgBr (1.4M solution in THF-toluene, 0.49 mL, 0.69 mmol) dropwise. The resulting mixture was stirred at −78 C. for 2 h and then it was allowed to warm to −20° C. over 2 h. The mixture was then quenched with 1 mL of 1 M NaHCO3, and then it was patitioned with ethyl acetate (20 mL) and 1 M NaHCO3 (5 mL). The organic phase was separated, washed (H2O brine), dried (MgSO4) and evaporated. Flash chromatography (SiO2/2-28% ethyl acetate-hexane) of the residue afforded 12-[4-deoxy -6-O-(tert-butyldiphenylsilyl)-2-O-benzyl-3-methyl-β-D-allopyranosyl]-2,3,9,10-tetrafluoro-12,13-dihydro-5H-indolo[2,3-a]pyrrolo[3,4-c]carbazole-5,7(6H)-dione (0.052 g, 43%) and then 12-[4-deoxy-6-O-(tert-butyldiphenylsilyl)-2-O-benzyl-3-methyl-β-D-glucopyranosyl]-2,3,9,10-tetrafluoro-12,13-dihydro-5H-indolo[2,3-a]pyrrolo[3,4-c]carbazole-5,7(6H)-dione (0.028 g, 23%); MS (ESI−) m/e 884 (M−H)−. To a cold (5° C.) solution of 12-[4-deoxy-6-O-(tert-butyldiphenylsilyl)-2-O-benzyl-3-methyl -β-D-allopyranosyl]-2,3,9,10-tetrafluoro-12,13-dihydro-5H-indolo[2,3-a]pyrrolo [3,4-c]carbazole-5,7(6H)-dione (0.050 g, 0.056 mmol) in 5 mL of MeCN under Ar was added Et3N.3HF (0.091 mL, 0.56 mmol) and the mixture was stirred at room temperature for 2 days. The resulting mixture was diluted with ethyl acetate, washed (1M NaHCO3, H2O, brine) dried (MgSO4) and evaporated. The residue was purified by prep tlc (SiO2/ethyl acetate-hexane, 3:2) to give 12-[4-deoxy-2-O-benzyl-3-methyl-β-D-allopyranosyl]-2,3,9,10-tetrafluoro-12,13-dihydro-5H-indolo[2,3-a]pyrrolo[3,4-c]carbazole-5,7(6H)-dione (0.026 g, 72%) as a yellow solid; MS (ESI−) m/e 646 (M−H)−.

Workup

  1. washwashed (1M NaHCO3, H2O, brine)
  2. dry with materialdried (MgSO4)
  3. customevaporated
  4. customThe residue was purified by prep tlc (SiO2/ethyl acetate-hexane, 3:2)

Sources & evidence

ORD record
ord-a22089377be741d9b0eac4de17b53469
Source dataset
uspto-grants-2005_02
Patent number
US06855698B2

Reaction notes

Loading…