1,2-Diiodoethane → 17-Ethyl-1,2,14-trihydroxy-12-[2'-(4"-(naphth-2-yl)-3"-methoxycyclohexyl)-1'-methylvinyl]-23,25-dimethoxy-13,19,21,27-tetramethyl-11,28-dioxa-4-azatricyclo[22.3.1.04,9]octacos-18-ene-3,10,16-trione

HRID 865568

反応式

HRID 865568 の反応式
ICCI.[Sm].C(=O)=O.CC(C)=O.[CH2:13]([CH:15]1[CH:41]=[C:40]([CH3:42])[CH2:39][CH:38]([CH3:43])[CH2:37][CH:36]([O:44][CH3:45])[CH:35]2[O:46][C:31]([OH:50])([CH:32]([CH3:49])[CH2:33][CH:34]2[O:47][CH3:48])[C:30](=[O:51])[C:29](=[O:52])[N:28]2[CH:23]([CH2:24][CH2:25][CH2:26][CH2:27]2)[C:22](=[O:53])[O:21][CH:20]([C:54]([CH3:74])=[CH:55][CH:56]2[CH2:61][CH2:60][CH:59]([C:62]3[CH:71]=[CH:70][C:69]4[C:64](=[CH:65][CH:66]=[CH:67][CH:68]=4)[CH:63]=3)[CH:58]([O:72][CH3:73])[CH2:57]2)[CH:19]([CH3:75])[CH:18]([OH:76])[CH2:17][C:16]1=[O:77])[CH3:14]>C1COCC1.C1COCC1.CO>[CH2:13]([CH:15]1[CH:41]=[C:40]([CH3:42])[CH2:39][CH:38]([CH3:43])[CH2:37][CH:36]([O:44][CH3:45])[CH:35]2[O:46][C:31]([OH:50])([CH:32]([CH3:49])[CH2:33][CH:34]2[O:47][CH3:48])[CH:30]([OH:51])[C:29](=[O:52])[N:28]2[CH:23]([CH2:24][CH2:25][CH2:26][CH2:27]2)[C:22](=[O:53])[O:21][CH:20]([C:54]([CH3:74])=[CH:55][CH:56]2[CH2:61][CH2:60][CH:59]([C:62]3[CH:71]=[CH:70][C:69]4[C:64](=[CH:65][CH:66]=[CH:67][CH:68]=4)[CH:63]=3)[CH:58]([O:72][CH3:73])[CH2:57]2)[CH:19]([CH3:75])[CH:18]([OH:76])[CH2:17][C:16]1=[O:77])[CH3:14]

参加物

7

反応物 4

HCID 122241,2-DiiodoethaneHCID 23951SamariumHCID 18522661Acetone cardiceHCID 5718413317-Ethyl-1,14-dihydroxy-12-[2'-(4"-(naphth-2-yl)-3"-methoxycyclohexyl)-1'-methylvinyl]-23,25-dimethoxy-13,19,21,27-tetramethyl-11,28-dioxa-4-azatricyclo[22.3.1.04,9]octacos-18-ene-2,3,10,16-tetraone

生成物 1

HCID 5712063717-Ethyl-1,2,14-trihydroxy-12-[2'-(4"-(naphth-2-yl)-3"-methoxycyclohexyl)-1'-methylvinyl]-23,25-dimethoxy-13,19,21,27-tetramethyl-11,28-dioxa-4-azatricyclo[22.3.1.04,9]octacos-18-ene-3,10,16-trione収率 22.3%

試薬・触媒・溶媒 2

HCID 8028Tetrahydrofuran溶媒2 回HCID 21899815MeOH tetrahydrofuran溶媒

反応条件

温度
-78 °C

実験手順

A solution of 1,2-diiodoethane (42 mg, 0.15 mmol) in dry THF (1 mL) was added dropwise to a stirred mixture of samarium metal (46.5 mg, 0.31 mmol) in dry THF (1 mL) and stirred for 1.5 hours. The reaction mixture was then cooled to -78° C. (dry ice/acetone) and treated with a solution of 17-ethyl-1,14-dihydroxy-12-[2'-(4"-(naphth-2-yl)-3"-methoxycyclohexyl)-1 '-methylvinyl]-23,25-dimethoxy-13,19,21,27-tetramethyl-11,28-dioxa-4-azatricyclo[22.3.1.04,9 ]octacos-18-ene-2,3,10,16-tetraone (100 mg, 0.109 mmol) in 1:1 THF/CH3OH. The mixture was maintained at -78° C. for 15 minutes then allowed to warm to room temperature. The reaction was quenched with cold saturated aqueous K2CO3 and quickly extracted with CH2Cl2. The extracts were combined, dried with Na2SO4, filtered and concentrated in vacuo. Purified by preparative TLC on silica gel (eluted with 7% CH3OH in CH2Cl2) to give 22 mg of 17-ethyl-1,2,14-trihydroxy-12-[2'-(4"-(naphth-2-yl)-3"-methoxycyclohexyl)-1'-methylvinyl]-23,25-dimethoxy-13,19,21,27-tetramethyl-11,28-dioxa-4-azatricyclo[22.3.1.04,9 ]octacos-18-ene-3,10,16-trione (1H NMR and mass spectral analysis are consistent with the desired structure).

後処理

  1. temperatureto warm to room temperature
  2. customThe reaction was quenched with cold saturated aqueous K2CO3
  3. extractionquickly extracted with CH2Cl2
  4. dry with materialdried with Na2SO4
  5. filtrationfiltered
  6. concentrationconcentrated in vacuo
  7. customPurified by preparative TLC on silica gel (eluted with 7% CH3OH in CH2Cl2)

出典と根拠

ORDレコード
ord-4a4b0ffbe16c49c2ac988f2403f5d38c
出典データセット
uspto-grants-1996_10
特許番号
US05565560

関連ノート

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