Triacetoxyperiodinane → HCID 24760921, compound

HRID 2261281Notes

Reaction equation

HRID 2261281 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:32](=[O:56])[C@@H:33]([NH:38][C:39](=[O:55])[C:40]3[CH:45]=[CH:44][C:43]([N:46]4[CH2:51][CH2:50][N:49]([CH2:52][CH2:53][CH3:54])[CH2:48][CH2:47]4)=[CH:42][CH:41]=3)[CH2:34][CH:35]([CH3:37])[CH3:36])[CH2:30][CH2:31][C@H:27]2[O:26][CH2:25]1>ClCCl>[CH3:37][CH:35]([CH3:36])[CH2:34][C@H:33]([NH:38][C:39](=[O:55])[C:40]1[CH:45]=[CH:44][C:43]([N:46]2[CH2:51][CH2:50][N:49]([CH2:52][CH2:53][CH3:54])[CH2:48][CH2:47]2)=[CH:42][CH:41]=1)[C:32](=[O:56])[N:29]1[CH2:30][CH2:31][C@H:27]2[O:26][CH2:25][C:24](=[O:23])[C@@H:28]12

Participants

4

Reactant 2

HCID 159087TriacetoxyperiodinaneHCID 86633304HCID 86633304, compound

Product 1

HCID 24760921HCID 24760921, compoundYield 323.4%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Procedure

Oxidation to Example 3 Dess-Martin periodinane (1.83 g, 4.30 mmol) was added to a stirred solution of N—((S)-1-((3R,3aR,6aR)-3-hydroxydihydro-2H-furo[3,2-b]pyrrol-4(5H,6H, 6aH)-yl)-4-methyl-1-oxopentan-2-yl)-4-(4-propylpiperazin-1-yl)benzamide (250 mg, 0.546 mmol) in dichloromethane (45 mL) under an atmosphere of argon. The mixture was stirred for 18.5 hours then diluted with dichloromethane (200 mL). The organic phase was washed with aqueous sodium hydroxide solution (1M, 70 mL) then the aqueous extracted with dichloromethane (75 mL). The organic layer was washed with aqueous sodium hydroxide solution (1M, 70 mL) then brine (70 mL), then dried (Na2SO4), filtered and reduced in vacuo to give Example 3 as a pale yellow solid (0.831 g, 82%). TLC (Rf=0.30, MeOH:CH2Cl2 1:9), analytical HPLC main peak, Rt=9.80 min., HPLC-MS 471.3 [M+H]+, 489.3 [M+H2O+H]+, 963.6 [2M+Na]+; [α]D21−92.8° (c=3.29, CHCl3); δH (500 MHz, CDCl3)-hydrate not assigned here 0.91 (3H, d, J=6.58 Hz, CH(CH3)2), 0.93 (3H, t, J=7.32 Hz, CH2CH3), 1.00 (3H, d, J=6.47 Hz, CH(CH3)2), 1.52-1.78 (5H, m, CH2CH(CH3)2 and CH2CH3), 2.06-2.15 (1H, m, NCH2CH2CH), 2.29 (1H, dd, J=13.69 and 6.09 Hz, NCH2CH2CH), 2.40-2.45 (2H, m, NCH2CH2CH3), 2.66 (4H, brt, J=4.80 Hz, CH2NCH2CH2CH3), 3.35 (4H, brt, J=5.01 Hz, CH2CH2NCH2CH2CH3), 3.55-3.62 (1H, m, NCH2CH2CH), 3.98 (1H, d, J=17.03 Hz, OCH2C═O), 4.14 (1H, d, J=16.96 Hz, OCH2C═O), 4.17 (1H, brt, J=8.89 Hz, NCH2CH2CH), 4.66 (1H, d, J=5.16 Hz, NCH2CH2CHCH), 4.89 (1H, t, J=4.35 Hz, NCH2CH2CHCH), 5.01-5.06 (1H, m, CHCH2CH(CH3)2), 6.79 (1H, d, J=8.45 Hz, NH), 6.87 (2H, brd, J=8.97 Hz, aromatic CH), 7.70 (2H, brd, J=8.94 Hz, aromatic CH); δC (125 MHz, CDCl3) 11.91 (CH2CH3), 19.95 (CH2CH3), 22.12/23.28 and 24.77 (CH(CH3)2), 32.48 (NCH2CH2CH), 42.67 (CH2CH(CH3)2), 45.60 (NCH2CH2CHCH), 47.72 (NCH2CH2NCH2CH2CH3), 49.52 (CHCH2CH(CH3)2), 52.89 (NCH2CH2NCH2CH2CH3), 60.58 (NCH2CH2CH3), 62.15 (NCH2CH2CHCH), 71.02 (OCH2C═O), 80.78 (NCH2CH2CHCH), 114.06/114.09/128.51 and 128.59 (aromatic CH), 123.26 (aromatic quaternary), 153.49 (aromatic quaternary), 166.78 (NHC═O), 172.41 (CH2NC═O), 208.43 (ketone C═O).

Workup

  1. washThe organic phase was washed with aqueous sodium hydroxide solution (1M, 70 mL)
  2. extractionthe aqueous extracted with dichloromethane (75 mL)
  3. washThe organic layer was washed with aqueous sodium hydroxide solution (1M, 70 mL)
  4. dry with materialbrine (70 mL), then dried (Na2SO4)
  5. filtrationfiltered

Sources & evidence

ORD record
ord-79350cd4f29943e2af8c27e073fa9682
Source dataset
uspto-grants-2010_12
Patent number
US07846935B2

Reaction notes

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