Hydrogen Peroxide → HCID 68008462, 화합물

HRID 1429099노트

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HRID 1429099 반응식
[C:1]([O:5][C:6]([NH:8][C@@H:9]1[C:23](=[O:24])[N:22]2[CH2:25][C@H:26]([O:28][C:29]3[N:30]=[C:31]4[C:36](=[C:37]5[C:42]=3[CH:41]=[CH:40][CH:39]=[CH:38]5)[CH:35]=[CH:34][CH:33]=[CH:32]4)[CH2:27][C@H:21]2[C:20](=[O:43])[NH:19][C@:18]2([C:45]([O:47][CH2:48][CH3:49])=[O:46])[CH2:44][C@H:17]2[CH:16]=[CH:15][CH2:14][CH2:13][CH2:12][CH2:11][CH2:10]1)=[O:7])([CH3:4])([CH3:3])[CH3:2].[O:50]1CCCC1.B.[OH-].[Na+].OO>O1CCCC1.C(OCC)(=O)C.O>[C:1]([O:5][C:6]([NH:8][C@@H:9]1[C:23](=[O:24])[N:22]2[CH2:25][C@H:26]([O:28][C:29]3[N:30]=[C:31]4[C:36](=[C:37]5[C:42]=3[CH:41]=[CH:40][CH:39]=[CH:38]5)[CH:35]=[CH:34][CH:33]=[CH:32]4)[CH2:27][C@H:21]2[C:20](=[O:43])[NH:19][C@:18]2([C:45]([O:47][CH2:48][CH3:49])=[O:46])[CH2:44][C@H:17]2[CH2:16][CH:15]([OH:50])[CH2:14][CH2:13][CH2:12][CH2:11][CH2:10]1)=[O:7])([CH3:4])([CH3:3])[CH3:2]

참가 물질

8

반응물 4

HCID 784Hydrogen PeroxideHCID 14798Sodium HydroxideHCID 2723981Borane;tetrahydrofuranHCID 68499992HCID 68499992, 화합물

생성물 1

HCID 68008462HCID 68008462, 화합물수율 32.3%

시약·촉매·용매 3

HCID 962Water용매HCID 8028Tetrahydrofuran용매HCID 8857Ethyl Acetate용매

실험 절차

To a solution of (2R,6S,13aS,14aR,16aS,Z)-ethyl 6-(tert-butoxycarbonylamino)-5,16-dioxo-2-(phenanthridin-6-yloxy)-1,2,3,5,6,7,8,9,10,11,13a,14,14a,15,16,16a-hexadecahydrocyclopropa[e]pyrrolo [1,2-a][1,4]diazacyclopentadecine-14a-carboxylate (Example 18a, 3.2 g, 4.77 mmol) in tetrahydrofuran (41.5 ml) at rt with a water bath was added dropwise borane tetrahydrofuran complex (1 M in tetrahydrofuran, 14.3 ml, 14.3 mmol) and stirred at room temperature for 1 h. The mixture was cooled to 0° C. and sodium hydroxide (11.5 ml, 28.6 mmol) was added dropwise followed by hydrogen peroxide (4.0 ml, 43 mmol), and the reaction mixture stirred for 1.5 h at 0° C. The mixture was diluted with ethyl acetate and water, and the organic layer was washed with saturated aqueous sodium chloride solution. The resulting solid was purified via flash chromatography on silica gel (5% methanol in dichloromethane) to provide the title compound (2R,6S,13aS,14aR,16aS)-ethyl 6-(tert-butoxycarbonylamino)-12-hydroxy-5,16-dioxo-2-(phenanthridin-6-yloxy)octadecahydrocyclopropa[e]pyrrolo[1,2-a][1,4]diazacyclopentadecine-14a-carboxylate (1.06 g, 1.539 mmol, 32.3% yield). The α-hydroxy analog (2R,6S,13R,13aR,14aR,16aS)-ethyl 6-(tert-butoxycarbonylamino)-13-hydroxy-5,16-dioxo-2-(phenanthridin-6-yloxy)octadecahydrocyclopropa[e]pyrrolo [1,2-a][1,4]diazacyclopentadecine-14a-carboxylate (0.7 g, 21% yield) was also isolated.

후처리

  1. temperatureThe mixture was cooled to 0° C.
  2. stirringthe reaction mixture stirred for 1.5 h at 0° C
  3. washthe organic layer was washed with saturated aqueous sodium chloride solution
  4. customThe resulting solid was purified via flash chromatography on silica gel (5% methanol in dichloromethane)

출처 및 근거

ORD 기록
ord-99600cb2db3d4dafba06c7aa2eedc11b
출처 데이터셋
uspto-grants-2015_01
특허 번호
US08937041B2

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