Methoxymethyl-triphenylphosphonium chloride → (R)-3-[(1R,4aR,5S,8aR)-5-(tert-butyldimethyl-silanyloxy)-8a-methyl-decahydro-naphthalen-1-yl]-butyraldehyde

HRID 1604832ノート

反応式

HRID 1604832 の反応式
[Cl-].C[O:3]C[P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.[Li][CH2:25][CH2:26][CH2:27][CH3:28].[C:29]([Si:33]([CH3:51])([CH3:50])[O:34][C@H:35]1[CH2:44][CH2:43][CH2:42][C@@:41]2([CH3:45])[C@H:36]1[CH2:37][CH2:38][CH2:39][C@@H:40]2[C@H](C)C=O)([CH3:32])([CH3:31])[CH3:30]>C1COCC1>[C:29]([Si:33]([CH3:50])([CH3:51])[O:34][C@H:35]1[CH2:44][CH2:43][CH2:42][C@@:41]2([CH3:45])[C@H:36]1[CH2:37][CH2:38][CH2:39][C@@H:40]2[C@H:27]([CH3:28])[CH2:26][CH:25]=[O:3])([CH3:31])([CH3:30])[CH3:32]

参加物

5

反応物 3

HCID 2723798Methoxymethyl-triphenylphosphonium chlorideHCID 57255936(S)-2-[(1R,4aR,5S,8aR)-5-(tert-butyldimethyl-silanyloxy)-8a-methyl-decahydro-naphthalen-1-yl]-propionaldehydeHCID 178418339Butyllithium

生成物 1

HCID 57316286(R)-3-[(1R,4aR,5S,8aR)-5-(tert-butyldimethyl-silanyloxy)-8a-methyl-decahydro-naphthalen-1-yl]-butyraldehyde

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒2 回

実験手順

A suspension of 6.54 g of (methoxymethyl)triphenylphosphonium chloride in 38 ml of abs. THF was cooled to -10° and treated with 11.3 ml of nBuLi (1.5 M, hexane). 15 minutes later, the deep red ylide solution was cooled down to -78° and 3.225 g of (S)-2-[(1R,4aR,5S,8aR)-5-(tert-butyldimethyl-silanyloxy)-8a-methyl-decahydro-naphthalen-1-yl]-propionaldehyde dissolved in 21 ml of abs. THF, were slowly added and the reaction mixture kept for 60 minutes at that temperature. Partition between hexane and EtOH/H2O=8/2, washing of the upper layer with EtOH/H2O=8/2, drying over sodium sulfate, evaporating i. V. and flash chromatography (SiO2, hexane/AcOEt=98/2) delivered 3.11 g of an enolether intermediate as E/Z-mixture, contaminated with some impurities which were removed after the next step. This enolether was hydrolyzed by dissolving it in 35 ml of THF containing 12.5 ml of 25% aq. HCl. After 2.5 h at ambient temperature, the reaction mixture was poured onto crushed ice, extracted with ether, washed with water and brine, dried over sodium sulfate and evaporated to dryness. Flash chromatography (SiO2, hexane/AcOEt=98/2) yielded 1.76 g of (R)-3-[(1R,4aR,5S,8aR)-5-(tert-butyldimethyl-silanyloxy)-8a-methyl-decahydro-naphthalen-1-yl]-butyraldehyde as colourless oil.

後処理

  1. temperature15 minutes later, the deep red ylide solution was cooled down to -78°
  2. customPartition between hexane and EtOH/H2O=8/2
  3. washwashing of the upper layer with EtOH/H2O=8/2
  4. dry with materialdrying over sodium sulfate
  5. customevaporating i
  6. customwere removed after the next step
  7. dissolutionby dissolving it in 35 ml of THF containing 12.5 ml of 25% aq. HCl
  8. waitAfter 2.5 h at ambient temperature
  9. additionthe reaction mixture was poured
  10. customonto crushed ice
  11. extractionextracted with ether
  12. washwashed with water and brine
  13. dry with materialdried over sodium sulfate
  14. customevaporated to dryness

出典と根拠

ORDレコード
ord-066e7d8f87cd4a6ea871bf421ad13729
出典データセット
uspto-grants-1999_11
特許番号
US05994569

反応ノート

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