N-(5-chloropyridin-2-yl)-1,1,1-trifluoro-N-trifluoromethanesulfonylmethanesulfonamide → (1R,3aS,5aR,5bR,7aR,11aR,11bR,13aR,13bR)-3a-((2-(N-(5-chloropyridin-2-yl)-1,1,1-trifluoromethylsulfonamido)ethyl)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

HRID 1401003

反応式

HRID 1401003 の反応式
[N:1]1([C@:4]23[CH2:30][CH2:29][C@@H:28]([C:31]([CH3:33])=[CH2:32])[C@@H:5]2[C@@H:6]2[C@@:19]([CH3:22])([CH2:20][CH2:21]3)[C@@:18]3([CH3:23])[C@@H:9]([C@:10]4([CH3:27])[C@@H:15]([CH2:16][CH2:17]3)[C:14]([CH3:25])([CH3:24])[C:13](=[O:26])[CH2:12][CH2:11]4)[CH2:8][CH2:7]2)[CH2:3][CH2:2]1.[Cl:34][C:35]1[CH:36]=[CH:37][C:38]([N:41]([S:49]([C:52]([F:55])([F:54])[F:53])(=[O:51])=[O:50])S(C(F)(F)F)(=O)=O)=[N:39][CH:40]=1.C[Si]([N-][Si](C)(C)C)(C)C.[K+]>C1COCC1>[F:53][C:52]([F:55])([F:54])[S:49]([O:26][C:13]1[C:14]([CH3:24])([CH3:25])[C@H:15]2[C@:10]([CH3:27])([CH2:11][CH:12]=1)[C@@H:9]1[C@:18]([CH3:23])([C@@:19]3([CH3:22])[C@H:6]([CH2:7][CH2:8]1)[C@H:5]1[C@H:28]([C:31]([CH3:33])=[CH2:32])[CH2:29][CH2:30][C@:4]1([NH:1][CH2:2][CH2:3][N:41]([C:38]1[CH:37]=[CH:36][C:35]([Cl:34])=[CH:40][N:39]=1)[S:49]([C:52]([F:53])([F:54])[F:55])(=[O:50])=[O:51])[CH2:21][CH2:20]3)[CH2:17][CH2:16]2)(=[O:51])=[O:50]

参加物

5

反応物 3

HCID 388544N-(5-chloropyridin-2-yl)-1,1,1-trifluoro-N-trifluoromethanesulfonylmethanesulfonamideHCID 3251421Potassium bis(trimethylsilyl)amideHCID 71698573(1R,3aS,5aR,5bR,7aR,11aR,11bR,13aR,13bR)-3a-(aziridin-1-yl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)octadecahydro-1H-cyclopenta[a]chrysen-9(5bH)-one

生成物 1

HCID 86692356(1R,3aS,5aR,5bR,7aR,11aR,11bR,13aR,13bR)-3a-((2-(N-(5-chloropyridin-2-yl)-1,1,1-trifluoromethylsulfonamido)ethyl)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

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒

反応条件

温度
-78 °C

実験手順

(1R,3aS,5aR,5bR,7aR,11aR,11bR,13aR,13bR)-3a-(aziridin-1-yl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)octadecahydro-1H-cyclopenta[a]chrysen-9(5bH)-one (353 mg, 0.781 mmol) was mixed with N-(5-chloropyridin-2-yl)-1,1,1-trifluoro-N-((trifluoromethyl)sulfonyl)methanesulfonamide (338 mg, 0.860 mmol) in THF (2 mL) under nitrogen. The solution was stirred at −78° C. under nitrogen. A 0.5 M stock solution of potassium bis(trimethylsilyl)amide (1.875 mL, 0.938 mmol) was added, and the mixture was stirred at −78° C. for an hour. The desired product was purified by silica gel chromatography eluted with mixture of ethyl acetate and hexanes (230 mg, 35%). MS: m/e 844.3/846.3 (M+H)+, 6.47 min (method 15). 1H NMR (400 MHz, CHLOROFORM-d) δ (key fingerprint signals) 8.45 (d, J=2.0 Hz, 1H), 7.76 (dd, J=8.7, 2.6 Hz, 1H), 7.48 (d, J=8.5 Hz, 1H), 5.57 (d, J=6.5 Hz, 1H), 4.80-4.57 (m, 3H), 3.71-3.65 (m, 1H), 2.80-2.73 (m, 1H), 2.73-2.49 (m, 2H), 2.45-2.29 (m, 1H), 2.26-2.12 (m, 2H), 2.08-1.94 (m, 2H), 1.93-1.80 (m, 2H), 1.80-1.72 (m, 3H), 1.71-1.65 (m, 6H). 19F NMR (376 MHz, CHLOROFORM-d) δ −74.84 (s), −74.85 (s).

後処理

  1. stirringthe mixture was stirred at −78° C. for an hour
  2. customThe desired product was purified by silica gel chromatography
  3. washeluted with mixture of ethyl acetate and hexanes (230 mg, 35%)
  4. customm/e 844.3/846.3 (M+H)+, 6.47 min (method 15)

出典と根拠

ORDレコード
ord-0593ddfbf50f41c39daeed2ddb2398fc
出典データセット
uspto-grants-2014_12
特許番号
US08906889B2

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