Triacetoxyperiodinane → 4-(4-isopropylpiperazin-1-yl)-N-((S)-1-((3aS,6R,6aS)-6-methoxy-3-oxodihydro-2H-furo[3,2-b]pyrrol-4(5H,6H,6aH)-yl)-4,4-dimethyl-1-oxopentan-2-yl)benzamide

HRID 1716469ノート

反応式

HRID 1716469 の反応式
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:59])[C@@H:35]([NH:41][C:42](=[O:58])[C:43]3[CH:48]=[CH:47][C:46]([N:49]4[CH2:54][CH2:53][N:52]([CH:55]([CH3:57])[CH3:56])[CH2:51][CH2:50]4)=[CH:45][CH:44]=3)[CH2:36][C:37]([CH3:40])([CH3:39])[CH3:38])[CH2:30][C@@H:31]([O:32][CH3:33])[C@H:27]2[O:26][CH2:25]1>ClCCl>[CH:55]([N:52]1[CH2:51][CH2:50][N:49]([C:46]2[CH:45]=[CH:44][C:43]([C:42]([NH:41][C@@H:35]([CH2:36][C:37]([CH3:40])([CH3:39])[CH3:38])[C:34]([N:29]3[CH2:30][C@@H:31]([O:32][CH3:33])[C@H:27]4[O:26][CH2:25][C:24](=[O:23])[C@@H:28]34)=[O:59])=[O:58])=[CH:48][CH:47]=2)[CH2:54][CH2:53]1)([CH3:57])[CH3:56]

参加物

4

反応物 2

HCID 159087TriacetoxyperiodinaneHCID 68510175N-((S)-1-((3R,3aR,6R,6aS)-3-hydroxy-6-methoxydihydro-2H-furo[3,2-b]pyrrol-4(5H,6H,6aH)-yl)-4,4-dimethyl-1-oxopentan-2-yl)-4-(4-isopropylpiperazin-1yl)benzamide

生成物 1

HCID 250068914-(4-isopropylpiperazin-1-yl)-N-((S)-1-((3aS,6R,6aS)-6-methoxy-3-oxodihydro-2H-furo[3,2-b]pyrrol-4(5H,6H,6aH)-yl)-4,4-dimethyl-1-oxopentan-2-yl)benzamide

試薬・触媒・溶媒 1

HCID 6344Dichloromethane溶媒2 回

実験手順

Dess-Martin periodinane (2.82 g, 6.66 mmol) was added to a stirred solution of N—((S)-1-((3R,3aR,6R,6aS)-3-hydroxy-6-methoxydihydro-2H-furo[3,2-b]pyrrol-4(5H,6H,6aH)-yl)-4,4-dimethyl-1-oxopentan-2-yl)-4-(4-isopropylpiperazin-1yl)benzamide (1.72 g, 3.33 mmol) in dichloromethane (65 mL) under an atmosphere of argon. The mixture was stirred for 18 hours then diluted with dichloromethane (300 mL). The organic phase was washed with aqueous sodium hydroxide solution (1M, 100 mL) then the aqueous extracted with dichloromethane (150 mL). The organic layer was washed with aqueous sodium hydroxide solution (1M, 100 mL) then brine (150 mL), then dried (Na2SO4), filtered and reduced in vacuo to give 4-(4-isopropylpiperazin-1-yl)-N—((S)-1-((3aS,6R,6aS)-6-methoxy-3-oxodihydro-2H-furo[3,2-b]pyrrol-4(5H,6H,6aH)-yl)-4,4-dimethyl-1-oxopentan-2-yl)benzamide a pale yellow solid (1.408 g, 82%). TLC (Rf=0.45, MeOH:CH2Cl2 1:19), analytical HPLC main peak, Rt=10.39 min., HPLC-MS 515.3 [M+H]+, 533.3 [M+H2O+H]+, 1051.6 [2M+Na]+; [□]D22−31.08° (c=3.7, CHCl3); δH (500 MHz, CDCl3) 0.99 (9H, s, C(CH3)3), 1.08 (6H, d, J=6.52 Hz, NCH(CH3)2), 1.68-1.74 (2H, m, CH2C(CH3)3), 2.65 (4H, brt, J=5.04 Hz, CH2NCH(CH3)2), 2.67-2.73 (1H, m, NCH(CH3)2), 3.29 (4H, brt, J=5.05 Hz, CH2CH2NCH(CH3)2), 3.49 (3H, s, OCH3), 3.61 (1H, dd, 5.35 Hz, NCH2CHOCH3), 4.00-4.04 (1H, m, CHOCH3), 4.09 (1H, d, J=16.89 Hz, OCH2C═O), 4.20 (1H, d, J=16.93 Hz, OCH2C═O), 4.27 (1H, dd, 5.88 Hz, NCH2CHOCH3), 4.74 (1H, d, J=6.86 Hz, OCH2(C═O)CH), 4.91 (1H, dd, 4.28 Hz, OCHCHOCH3), 4.94-5.00 (1H, m, CHCH2C(CH3)3), 6.61 (1H, d, J=8.69 Hz, NH), 6.84 (2H, brd, J=8.95 Hz, aromatic CH), 7.65 (2H, brd, J=8.91 Hz, aromatic CH); δC (125 MHz, CDCl3) 18.53 (NCH(CH3)2), 29.75/29.80 (C(CH3)3), 30.75/30.77 (C(CH3)3), 46.53 (CH2C(CH3)3), 47.02 (NCH2CH2NCH(CH3)2), 48.24 (CHCH2C(CH3)3), 48.43 (NCH2CH2NCH(CH3)2), 49.76 (NCH2CHOCH3), 54.49 (NCH(CH3)2), 58.23 (OCH3), 60.49 (OCH2C(═O)CH), 71.45 (OCH2C═O), 78.84 (CHOCH3), 80.25 (OCHCHOCH3), 114.01/114.10/128.49 and 129.83 (aromatic CH), 123.08 (aromatic quaternary), 153.55 (aromatic quaternary), 166.69 (NHC═O), 173.53 (CH2NC═O), 207.93 (ketone C═O).

後処理

  1. washThe organic phase was washed with aqueous sodium hydroxide solution (1M, 100 mL)
  2. extractionthe aqueous extracted with dichloromethane (150 mL)
  3. washThe organic layer was washed with aqueous sodium hydroxide solution (1M, 100 mL)
  4. dry with materialbrine (150 mL), then dried (Na2SO4)
  5. filtrationfiltered

出典と根拠

ORDレコード
ord-11804fe727b04256a41a1c298bac0a3c
出典データセット
uspto-grants-2010_09
特許番号
US07803803B2

反応ノート

読み込み中…