Sodium Carbonate Monohydrate → HCID 86692321, 화합물

HRID 1400975노트

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HRID 1400975 반응식
FC(F)(F)S(O[C:7]1[C:8]([CH3:36])([CH3:35])[C@H:9]2[C@:22]([CH3:25])([CH2:23][CH:24]=1)[C@@H:21]1[C@:12]([CH3:34])([C@@:13]3([CH3:33])[C@H:18]([CH2:19][CH2:20]1)[C@H:17]1[C@H:26]([C:29]([CH3:31])=[CH2:30])[CH2:27][CH2:28][C@:16]1([NH2:32])[CH2:15][CH2:14]3)[CH2:11][CH2:10]2)(=O)=O.CC1(C)C(C)(C)OB([C:47]2[CH2:52][CH2:51][CH:50]([C:53]([O:55][CH3:56])=[O:54])[CH2:49][CH:48]=2)O1.O.C(=O)([O-])[O-].[Na+].[Na+]>O1CCOCC1.O.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[NH2:32][C@:16]12[CH2:28][CH2:27][C@@H:26]([C:29]([CH3:31])=[CH2:30])[C@@H:17]1[C@@H:18]1[C@@:13]([CH3:33])([CH2:14][CH2:15]2)[C@@:12]2([CH3:34])[C@@H:21]([C@:22]3([CH3:25])[C@@H:9]([CH2:10][CH2:11]2)[C:8]([CH3:35])([CH3:36])[C:7]([C:47]2[CH2:52][CH2:51][CH:50]([C:53]([O:55][CH3:56])=[O:54])[CH2:49][CH:48]=2)=[CH:24][CH2:23]3)[CH2:20][CH2:19]1

참가 물질

7

반응물 3

HCID 2735133Sodium Carbonate MonohydrateHCID 66980107Methyl 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)cyclohex-3-enecarboxylateHCID 71698571(1R,3aS,5aR,5bR,7aR,11aR,11bR,13aR,13bR)-3a-amino-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysen-9-yl trifluoromethanesulfonate

생성물 1

HCID 86692321HCID 86692321, 화합물수율 32.8%

시약·촉매·용매 3

HCID 178418397HCID 178418397, 화합물촉매HCID 962Water용매HCID 312751,4-Dioxane용매

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온도
85 °C

실험 절차

To a sealable vial containing (1R,3aS,5aR,5bR,7aR,11aR,11bR,13aR,13bR)-3a-amino-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysen-9-yl trifluoromethanesulfonate (0.109 g, 0.195 mmol) was added methyl 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)cyclohex-3-enecarboxylate (0.078 g, 0.293 mmol), sodium carbonate hydrate (0.073 g, 0.586 mmol), and tetrakis(triphenylphosphine)palladium(0) (6.77 mg, 5.86 mmol). The mixture was diluted with 1,4-dioxane (2 mL) and water (0.5 mL) then was flushed with nitrogen, sealed and heated to 85° C. in an oil bath. After 20.5 h, the mixture was cooled to rt, diluted with water (10 mL) and extracted with dichloromethane (3×10 mL). The combined organic layers were dried with sodium sulfate. The drying agent was removed by filtration and the filtrate was concentrated under reduced pressure. The residue was adsorbed to silica gel and purified by chromatography using a 12 g Thomson silica gel column and a 10%-80% ethyl acetate in hexanes gradient. The fractions containing the expected product were combined and concentrated under reduced pressure to give methyl 4-((1R,3 aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-3a-amino-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysen-9-yl)cyclohex-3-enecarboxylate (0.035 g, 0.064 mmol, 32.7% yield) as an off-white solid. 1H NMR (400 MHz, chloroform-d) δ=5.35 (br. s., 1H), 5.19 (d, J=5.8 Hz, 1H), 4.73 (s, 1H), 4.60 (br. s., 1H), 3.69 (s, 3H), 2.55 (td, J=10.7, 5.1 Hz, 2H), 2.31 (d, J=2.3 Hz, 2H), 2.22-1.94 (m, 6H), 1.70 (s, 3H), 1.07 (s, 3H), 1.79-0.81 (m, 34H).

후처리

  1. customthen was flushed with nitrogen
  2. customsealed
  3. temperaturethe mixture was cooled to rt
  4. additiondiluted with water (10 mL)
  5. extractionextracted with dichloromethane (3×10 mL)
  6. dry with materialThe combined organic layers were dried with sodium sulfate
  7. customThe drying agent was removed by filtration
  8. concentrationthe filtrate was concentrated under reduced pressure
  9. custompurified by chromatography
  10. additionThe fractions containing the expected product
  11. concentrationconcentrated under reduced pressure

출처 및 근거

ORD 기록
ord-8284a947880a4b54b87b73439121bb00
출처 데이터셋
uspto-grants-2014_12
특허 번호
US08906889B2

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