N-[(E)-3-methylbutan-2-ylideneamino]-2,4,6-tri(propan-2-yl)benzenesulfonamide → (S)-tert-butyl 1-(tert-butyldimethylsilyloxy)but-3-en-2-yl(4-methyl-3-methylene-2-oxopentyl)carbamate

HRID 627091ノート

反応式

HRID 627091 の反応式
[CH:1]([C:4]1[CH:9]=C(C(C)C)C=C(C(C)C)[C:5]=1S(N/N=C(/C(C)C)\C)(=O)=O)(C)[CH3:2].C([Li])CCC.[Si:31]([O:38][CH2:39][C@@H:40]([N:43]([CH2:51][C:52](N(OC)C)=[O:53])[C:44](=[O:50])[O:45][C:46]([CH3:49])([CH3:48])[CH3:47])[CH:41]=[CH2:42])([C:34]([CH3:37])([CH3:36])[CH3:35])([CH3:33])[CH3:32]>CCCCCC.CN(CCN(C)C)C>[Si:31]([O:38][CH2:39][C@@H:40]([N:43]([CH2:51][C:52](=[O:53])[C:1](=[CH2:2])[CH:4]([CH3:9])[CH3:5])[C:44](=[O:50])[O:45][C:46]([CH3:48])([CH3:49])[CH3:47])[CH:41]=[CH2:42])([C:34]([CH3:35])([CH3:36])[CH3:37])([CH3:32])[CH3:33]

参加物

6

反応物 3

HCID 12563993N-[(E)-3-methylbutan-2-ylideneamino]-2,4,6-tri(propan-2-yl)benzenesulfonamide2 回HCID 89855339(S)-tert-butyl 1-(tert-butyldimethylsilyloxy)but-3-en-2-yl(2-(methoxy(methyl)amino)-2-oxoethyl)carbamate2 回HCID 178418339Butyllithium

生成物 1

HCID 131735279(S)-tert-butyl 1-(tert-butyldimethylsilyloxy)but-3-en-2-yl(4-methyl-3-methylene-2-oxopentyl)carbamate

試薬・触媒・溶媒 2

HCID 8037N,N,N',N'-Tetramethylethylenediamine溶媒HCID 8058Hexane溶媒2 回

反応条件

温度
-78 °C

実験手順

To a suspension of (E)-2,4,6-triisopropyl-N′-(3-methylbutan-2-ylidene)benzenesulfonohydrazide (Intermediate 33, 8 g, 21.82 mmol) in hexane (65 mL) and TMEDA (6.50 mL) at −78° C. was added dropwise n-butyllithium (1.6M in hexanes) (34.1 mL, 54.56 mmol). The reaction mixture turned orange and was stirred for 30 minutes at −78° C., then was warmed to 0° C. and bubbling started immediately. The suspension became a yellow solution. After ˜15 minutes the bubbling stopped and (S)-tert-butyl 1-(tert-butyldimethylsilyloxy)but-3-en-2-yl(2-(methoxy(methyl)-amino)-2-oxoethyl)carbamate (Intermediate 5, 4.39 g, 10.91 mmol) was added as a solution in hexane (2 mL). After ˜15 minutes LC/MS shows desired product and no remaining Weinreb amide starting material. The reaction mixture was quenched with saturated sodium bicarbonate and extracted with ether twice. The ether extracts were dried over magnesium sulfate, filtered and concentrated to afford a yellow oil. Silica gel chromatography (0%-10% ethyl acetate/hexanes) afforded the desired product (2.219 g, 49.4%) as a light yellow oil.

後処理

  1. temperaturewas warmed to 0° C.
  2. custombubbling
  3. waitAfter ˜15 minutes the bubbling stopped
  4. waitAfter ˜15 minutes LC/MS shows

出典と根拠

ORDレコード
ord-8be8cd70b3784a9d9f31083787d009c0
出典データセット
uspto-grants-2016_04
特許番号
US09309245B2

反応ノート

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