Methanesulfonic Acid → HCID 59557749、化合物

HRID 1175278ノート

反応式

HRID 1175278 の反応式
Br[C:2]1[CH:7]=[CH:6][C:5]([Cl:8])=[C:4]([CH2:9][C:10]2[CH:15]=[CH:14][C:13]([CH2:16][O:17][CH:18]3[CH2:20][CH2:19]3)=[CH:12][CH:11]=2)[CH:3]=1.[Li][CH2:22]CCC.C[Si](C)(C)[O:28][C@@H:29]1[C@@H:34]([O:35][Si](C)(C)C)[C@H:33]([O:40][Si](C)(C)C)[C@@H:32]([CH2:45][O:46][Si](C)(C)C)[O:31][C:30]1=[O:51].CS(O)(=O)=O>C1(C)C=CC=CC=1.C1COCC1.C1(C)C=CC=CC=1.CO>[Cl:8][C:5]1[CH:6]=[CH:7][C:2]([C:30]2([O:51][CH3:22])[C@H:29]([OH:28])[C@@H:34]([OH:35])[C@H:33]([OH:40])[C@@H:32]([CH2:45][OH:46])[O:31]2)=[CH:3][C:4]=1[CH2:9][C:10]1[CH:15]=[CH:14][C:13]([CH2:16][O:17][CH:18]2[CH2:20][CH2:19]2)=[CH:12][CH:11]=1

参加物

8

反応物 4

HCID 6395Methanesulfonic AcidHCID 10994280(3R,4S,5R,6R)-3,4,5-Tris-trimethylsilanyloxy-6-trimethylsilanyloxymethyl-tetrahydro-pyran-2-onHCID 595577574-Bromo-1-chloro-2-(4-(cyclopropoxymethyl)benzyl)benzeneHCID 178418339Butyllithium

生成物 1

HCID 59557749HCID 59557749、化合物

試薬・触媒・溶媒 3

HCID 887Methanol溶媒HCID 1140Toluene溶媒HCID 22635083Tetrahydrofuran toluene溶媒

反応条件

温度
-65 °C

実験手順

To a solution of 4-bromo-1-chloro-2-(4-(2-cyclopropoxymethyl)benzyl)benzene (0.6 g, 1.71 mmol) in anhydrous toluene/THF (6 mL, v/v=2:1) was added dropwise n-BuLi (2.5 M in hexane, 0.82 mL) at −65° C., and the mixture was stirred for 30 min at −65° C. Then a −65° C. solution of (3R,4S,5R,6R)-3,4,5-tris(trimethylsilyloxy)-6-((trimethylsilyloxy)methyl)tetrahydro-2H-pyran-2-one (0.87 g, 1.88 mmol) in toluene (6 mL) was added dropwise over 15 min. The mixture was stirred at −65° C. for 3.5 h until starting material was consumed. The reaction was quenched with methanesulfonic acid (0.23 mL, 3.58 mmol) in methanol (6 mL), and the mixture was allowed to warm to room temperature and stirred overnight. The reaction was quenched with saturated sodium bicarbonate, the organic phase was separated and the aqueous phase was extracted with ethyl acetate. The combined organic phases were washed with saturated bicarbonate, then with water, and then with brine, and dried over sodium sulfate. Removal of the volatiles afforded a residue (0.75 g), which was used in the next step without further purification.

後処理

  1. stirringThe mixture was stirred at −65° C. for 3.5 h
  2. customwas consumed
  3. temperatureto warm to room temperature
  4. stirringstirred overnight
  5. customThe reaction was quenched with saturated sodium bicarbonate
  6. customthe organic phase was separated
  7. extractionthe aqueous phase was extracted with ethyl acetate
  8. washThe combined organic phases were washed with saturated bicarbonate
  9. dry with materialwith water, and then with brine, and dried over sodium sulfate
  10. customRemoval of the volatiles

出典と根拠

ORDレコード
ord-9f38415cf49e4c1593839545a50c330b
出典データセット
uspto-grants-2010_11
特許番号
US07838499B2

反応ノート

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