Lithium Hexamethyldisilazide → Methyl 4-{2-(3-bromophenyl)-3-[(4-methoxybenzyl)oxy]-1-methyl-3-oxopropyl}benzoate

HRID 1880601ノート

反応式

HRID 1880601 の反応式
[Li+].C[Si]([N-][Si](C)(C)C)(C)C.[Br:11][C:12]1[CH:13]=[C:14]([CH2:18][C:19]([O:21][CH2:22][C:23]2[CH:28]=[CH:27][C:26]([O:29][CH3:30])=[CH:25][CH:24]=2)=[O:20])[CH:15]=[CH:16][CH:17]=1.Br[CH:32]([C:34]1[CH:43]=[CH:42][C:37]([C:38]([O:40][CH3:41])=[O:39])=[CH:36][CH:35]=1)[CH3:33]>C1COCC1>[Br:11][C:12]1[CH:13]=[C:14]([CH:18]([C:19]([O:21][CH2:22][C:23]2[CH:24]=[CH:25][C:26]([O:29][CH3:30])=[CH:27][CH:28]=2)=[O:20])[CH:32]([C:34]2[CH:43]=[CH:42][C:37]([C:38]([O:40][CH3:41])=[O:39])=[CH:36][CH:35]=2)[CH3:33])[CH:15]=[CH:16][CH:17]=1

参加物

5

反応物 3

HCID 2733832Lithium HexamethyldisilazideHCID 12342351Methyl 4-(1-bromoethyl)benzoateHCID 866195534-Methoxybenzyl (3-bromophenyl)acetate

生成物 1

HCID 67262891Methyl 4-{2-(3-bromophenyl)-3-[(4-methoxybenzyl)oxy]-1-methyl-3-oxopropyl}benzoate

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒2 回

実験手順

LHMDS (1.0M THF, 2.6 mL) was added dropwise to a −78° C. THF (4 mL) solution containing the intermediate from Step A (0.827 g, 2.47 mmol). After stirring 10 minutes a THF (4 mL) solution containing methyl 4-(1-bromoethyl)benzoate (0.6 g, 2.47 mmol) was added dropwise. The solution was allowed to warm to room temperature. After 1.5 hours the solution was partitioned between ethyl acetate and aqueous 1N HCl. The organic phase was washed with water, brine and dried over magnesium sulfate. The solution was filtered and the residue purified by silica gel chromatography using a hexanes/ethyl acetate gradient to give the title compounds as a 1.67/1 mixture of diastereomers. 1H NMR (400 MHz, CDCl3): selected data δ 5.16 (d, J=12.0 Hz); 5.01 (d, J=12.0 Hz); 4.82 (d, J=12.0 Hz); 4.64 (d, J=11.9 Hz); 1.34 (d, J=6.8 Hz); 1.02 (d, J=7.0 Hz). Minor diastereomer: LCMS1 4.08 min (N+Na)=519. Major diastereomer: LCMS1 4.19 min (M+Na)=519.

後処理

  1. additionwas added dropwise
  2. customAfter 1.5 hours the solution was partitioned between ethyl acetate and aqueous 1N HCl
  3. washThe organic phase was washed with water, brine
  4. dry with materialdried over magnesium sulfate
  5. filtrationThe solution was filtered
  6. customthe residue purified by silica gel chromatography

出典と根拠

ORDレコード
ord-660ecd5a169f4952aea7f4d8953aa2b1
出典データセット
uspto-grants-2012_11
特許番号
US08318760B2

反応ノート

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