Hydrogen Peroxide → 2-[(tert-butyldimethylsilyl)oxy]-3-[(3R)-12-[[4-(morpholin-4-yl)cyclohexyl]amino]-7-thia-9,11-diazatricyclo[6.4.0.0[2,6]]dodeca-1(12),2(6),8,10-tetraen-3-yl]propanamide

HRID 1503988Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1503988
[Si:1]([O:8][CH:9]([CH2:12][C@H:13]1[CH2:24][CH2:23][C:22]2[S:21][C:20]3[C:15](=[C:16]([NH:25][CH:26]4[CH2:31][CH2:30][CH:29]([N:32]5[CH2:37][CH2:36][O:35][CH2:34][CH2:33]5)[CH2:28][CH2:27]4)[N:17]=[CH:18][N:19]=3)[C:14]1=2)[C:10]#[N:11])([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2].[OH:38][Li].O.OO>CO>[Si:1]([O:8][CH:9]([CH2:12][C@H:13]1[CH2:24][CH2:23][C:22]2[S:21][C:20]3[C:15](=[C:16]([NH:25][CH:26]4[CH2:27][CH2:28][CH:29]([N:32]5[CH2:33][CH2:34][O:35][CH2:36][CH2:37]5)[CH2:30][CH2:31]4)[N:17]=[CH:18][N:19]=3)[C:14]1=2)[C:10]([NH2:11])=[O:38])([C:4]([CH3:6])([CH3:7])[CH3:5])([CH3:3])[CH3:2]

Komponenten

5

Edukt 3

HCID 784Hydrogen PeroxideHCID 168937Lithium hydroxide, monohydrateHCID 866951442-[(tert-butyldimethylsilyl)oxy]-3-[(3R)-12-[[4-(morpholin-4-yl)cyclohexyl]amino]-7-thia-9,11-diazatricyclo[6.4.0.0[2,6]]dodeca-1(12),2 (6),8,10-tetraen-3-yl]propanenitrile

Produkt 1

HCID 866951432-[(tert-butyldimethylsilyl)oxy]-3-[(3R)-12-[[4-(morpholin-4-yl)cyclohexyl]amino]-7-thia-9,11-diazatricyclo[6.4.0.0[2,6]]dodeca-1(12),2(6),8,10-tetraen-3-yl]propanamideAusbeute 70,4 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 887MethanolLösungsmittel

Reaktionsbedingungen

Temperatur
0 °C

Versuchsvorschrift

To a solution of 2-[(tert-butyldimethylsilyl)oxy]-3-[(3R)-12-[[4-(morpholin-4-yl)cyclohexyl]amino]-7-thia-9,11-diazatricyclo[6.4.0.0[2,6]]dodeca-1(12),2(6),8,10-tetraen-3-yl]propanenitrile (180 mg, 0.33 mmol, 1.00 equiv) in methanol (5 mL) was added LiOH.H2O (40 mg, 0.95 mmol, 3.00 equiv) and 0.5 mL of H2O2 (30%) at 0° C. The resulting solution was stirred for 1 h at 0° C. and then quenched with saturated aqueous Na2SO3, diluted with DCM (30 mL), washed with brine, dried over anhydrous sodium sulfate and concentrated under vacuum. The residue was applied onto a silica gel column with dichloromethane/methanol (20:1) to give 130 mg (70%) of 2-[(tert-butyldimethylsilyl)oxy]-3-[(3R)-12-[[4-(morpholin-4-yl)cyclohexyl]amino]-7-thia-9,11-diazatricyclo[6.4.0.0[2,6]]dodeca-1(12),2(6),8,10-tetraen-3-yl]propanamide as a white solid. MS: m/z 560 (M+H)+.

Aufarbeitung

  1. customquenched with saturated aqueous Na2SO3
  2. additiondiluted with DCM (30 mL)
  3. washwashed with brine
  4. dry with materialdried over anhydrous sodium sulfate
  5. concentrationconcentrated under vacuum

Quellen und Nachweise

ORD-Eintrag
ord-74243aeb27c54f1c91d47faec9d14311
Quelldatensatz
uspto-grants-2015_12
Patentnummer
US09212190B2

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