Trifluoroacetic acid → tert-butyl (3RS,4RS)-4-[4-(2-hydroxy-ethyl)-phenyl]-3-[4-(2-trimethylsilanyl-ethoxymethoxy)-naphthalen-2-ylmethoxy]-piperidine-1-carboxylate

HRID 1858733ノート

反応式

HRID 1858733 の反応式
[CH3:1][Si:2]([CH3:62])([CH3:61])[CH2:3][CH2:4][O:5][CH2:6][O:7][C:8]1[C:17]2[C:12](=[CH:13][CH:14]=[CH:15][CH:16]=2)[CH:11]=[C:10]([CH2:18][O:19][CH:20]2[CH:25]([C:26]3[CH:31]=[CH:30][C:29]([CH2:32][CH2:33][O:34]C(C4C=CC=CC=4)(C4C=CC=CC=4)C4C=CC=CC=4)=[CH:28][CH:27]=3)[CH2:24][CH2:23][N:22]([C:54]([O:56][C:57]([CH3:60])([CH3:59])[CH3:58])=[O:55])[CH2:21]2)[CH:9]=1.FC(F)(F)C(O)=O.FC(F)(F)C(OC(=O)C(F)(F)F)=O.C(N(CC)CC)C>C(Cl)Cl.CO>[OH:34][CH2:33][CH2:32][C:29]1[CH:28]=[CH:27][C:26]([CH:25]2[CH2:24][CH2:23][N:22]([C:54]([O:56][C:57]([CH3:60])([CH3:59])[CH3:58])=[O:55])[CH2:21][CH:20]2[O:19][CH2:18][C:10]2[CH:9]=[C:8]([O:7][CH2:6][O:5][CH2:4][CH2:3][Si:2]([CH3:1])([CH3:62])[CH3:61])[C:17]3[C:12](=[CH:13][CH:14]=[CH:15][CH:16]=3)[CH:11]=2)=[CH:31][CH:30]=1

参加物

7

反応物 4

HCID 6422Trifluoroacetic acidHCID 8471TriethylamineHCID 9845Trifluoroacetic anhydrideHCID 54268675tert-butyl (3RS,4RS)-3-[4-(2-trimethylsilanyl-ethoxymethoxy)-naphthalen-2-ylmethoxy]-4-[4-(2-trityloxy-ethyl)-phenyl]-piperidine-1-carboxylate

生成物 1

HCID 86604449tert-butyl (3RS,4RS)-4-[4-(2-hydroxy-ethyl)-phenyl]-3-[4-(2-trimethylsilanyl-ethoxymethoxy)-naphthalen-2-ylmethoxy]-piperidine-1-carboxylate収率 98.9%

試薬・触媒・溶媒 2

HCID 887Methanol溶媒HCID 6344Dichloromethane溶媒2 回

反応条件

温度
0 °C

実験手順

Selective cleavage of the trityl group was effected analogously to the procedure published by E. Krainer et al. in Tetrahedron Letters 1993, 1713-1716 by treating a solution of 780 mg (0.92 mmol) of tert-butyl (3RS,4RS)-3-[4-(2-trimethylsilanyl-ethoxymethoxy)-naphthalen-2-ylmethoxy]-4-[4-(2-trityloxy-ethyl)-phenyl]-piperidine-1-carboxylate in 15 ml of methylene chloride with a solution of 436 mg (3.68 mmol) of trifluoroacetic acid and 803 mg (3.68 mmol) of trifluoroacetic anhydride in 2 ml of methylene chloride. After 30 seconds the reaction mixture was cooled to 0° C. and treated with 4 ml of triethylamine. After 5 minutes 10 ml of methanol were added and the mixture was stirred for 10 minutes. Subsequently, the mixture was washed with saturated sodium hydrogen carbonate solution and the aqueous phase was thereafter back-extracted with 10 ml of methylene chloride. The combined organic phases were dried over sodium sulphate and then evaporated under reduced pressure. The crude product was chromatographed on silica gel using a 4:1 mixture of hexane and ethyl acetate as the eluent. There were obtained 553 mg of tert-butyl (3RS,4RS)-4-[4-(2-hydroxy-ethyl)-phenyl]-3-[4-(2-trimethylsilanyl-ethoxymethoxy)-naphthalen-2-ylmethoxy]-piperidine-1-carboxylate as a colourless oil.

後処理

  1. washSubsequently, the mixture was washed with saturated sodium hydrogen carbonate solution
  2. extractionthe aqueous phase was thereafter back-extracted with 10 ml of methylene chloride
  3. dry with materialThe combined organic phases were dried over sodium sulphate
  4. customevaporated under reduced pressure
  5. customThe crude product was chromatographed on silica gel using
  6. additiona 4:1 mixture of hexane and ethyl acetate as the eluent

出典と根拠

ORDレコード
ord-845326a38f5b41a3a3f42060cc59af7f
出典データセット
uspto-grants-2000_11
特許番号
US06150526

反応ノート

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