(3S,4S,6R)-(-)-8-(benzyloxy)-6-(tert-butyldimethylsilyloxy)-3-methyloct-1-en-4-ol | 912805-57-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (3S,4S,6R)-(-)-8-(benzyloxy)-6-(tert-butyldimethylsilyloxy)-3-methyloct-1-en-4-ol
• 英文别名: (3S,4S,6R)-6-[tert-butyl(dimethyl)silyl]oxy-3-methyl-8-phenylmethoxyoct-1-en-4-ol
• CAS: 912805-57-3
• 化学式: C₂₂H₃₈O₃Si
• 分子量: 378.627
• InChiKey: PNFDDBOWOIHXFJ-TYPHKJRUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.56
• 重原子数：
  26
• 可旋转键数：
  12
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.64
• 拓扑面积：
  38.7
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (3S,4S,6R)-(-)-8-(benzyloxy)-6-(tert-butyldimethylsilyloxy)-3-methyloct-1-en-4-ol 在 palladium on activated charcoal ruthenium trichloride 、 sodium periodate 、 氢气 、 三乙胺 作用下， 以 甲醇 、 四氯化碳 、 二氯甲烷 、 水 、 甲苯 、 乙腈 为溶剂， 反应 25.8h， 生成
  参考文献：
  名称：

  Synthetic Studies of Complex Immunostimulants from Quillaja saponaria:  Synthesis of the Potent Clinical Immunoadjuvant QS-21A_api

  摘要：

  QS-21 is one of the most promising new adjuvants for immune response potentiation and dose-sparing in vaccine therapy given its exceedingly high level of potency and its favorable toxicity profile. Melanoma, breast cancer, small cell lung cancer, prostate cancer, HIV-1, and malaria are among the numerous maladies targeted in more than 80 recent and ongoing vaccine therapy clinical trials involving QS-21 as a critical adjuvant component for immune response augmentation. QS-21 is a natural product immunostimulatory adjuvant, eliciting both T-cell- and antibody-mediated immune responses with microgram doses. Herein is reported the synthesis of QS-21A(api) in a highly modular strategy, applying novel glycosylation methodologies to a convergent construction of the potent saponin immunostimulant. The chemical synthesis of QS-21 offers unique opportunities to probe its mode of biological action through the preparation of otherwise unattainable nonnatural saponin analogues.

  DOI：

  10.1021/ja062364i
• 作为产物：
  描述：

  isobutyl 5-(benzyloxy)-3-oxopentanoate 在 Ru₂Cl₂[(R)-BINAP]2*Et₃N 咪唑 、 正丁基锂 、 potassium tert-butylate 、 氢气 、 二异丁基氢化铝 作用下， 以 四氢呋喃 、 甲醇 、 N,N-二甲基甲酰胺 、 甲苯 、 Petroleum ether 为溶剂， -78.0~23.0 ℃ 、5.72 MPa 条件下， 反应 89.58h， 生成 (3S,4S,6R)-(-)-8-(benzyloxy)-6-(tert-butyldimethylsilyloxy)-3-methyloct-1-en-4-ol
  参考文献：
  名称：

  Synthetic Studies of Complex Immunostimulants from Quillaja saponaria:  Synthesis of the Potent Clinical Immunoadjuvant QS-21A_api

  摘要：

  QS-21 is one of the most promising new adjuvants for immune response potentiation and dose-sparing in vaccine therapy given its exceedingly high level of potency and its favorable toxicity profile. Melanoma, breast cancer, small cell lung cancer, prostate cancer, HIV-1, and malaria are among the numerous maladies targeted in more than 80 recent and ongoing vaccine therapy clinical trials involving QS-21 as a critical adjuvant component for immune response augmentation. QS-21 is a natural product immunostimulatory adjuvant, eliciting both T-cell- and antibody-mediated immune responses with microgram doses. Herein is reported the synthesis of QS-21A(api) in a highly modular strategy, applying novel glycosylation methodologies to a convergent construction of the potent saponin immunostimulant. The chemical synthesis of QS-21 offers unique opportunities to probe its mode of biological action through the preparation of otherwise unattainable nonnatural saponin analogues.

  DOI：

  10.1021/ja062364i

文献信息

• Tetrahydropyran Synthesis by Intramolecular Conjugate Addition to Enones: Synthesis of the Clavosolide Tetrahydropyran Ring
  作者：Roderick Bates、Ping Song

  DOI：10.1055/s-0030-1257890

  日期：2010.9

  The synthesis of a tetrahydropyran intermediate for ­clavosolide A is reported, employing a combination of cross-­metathesis and intramolecular oxa-Michael addition. The intramolecular oxa-Michael addition to α,β-unsaturated esters requires the use of strong bases and can result in either modest yields or stereoisomeric mixtures, and can be highly variable according to the substrate structure. In contrast

  据报道，通过交叉复分解和分子内的氧杂-迈克尔加成反应，合成了用于clavosolide A的四氢吡喃中间体。α，β-不饱和酯的分子内oxa-Michael加成需要使用强碱，并可能导致适度的收率或立体异构体混合物，并且根据底物结构可能存在很大差异。相反，相应的酮在非常温和的条件下环化，直接得到2，6-顺式异构体。使用适当取代的酮可以有效地转化成酯。 迈克尔加成-串联反应-环化
• Synthetic Studies of Complex Immunostimulants from <i>Quillaja saponaria</i>:  Synthesis of the Potent Clinical Immunoadjuvant QS-21A_a_pi
  作者：Yong-Jae Kim、Pengfei Wang、Mauricio Navarro-Villalobos、Bridget D. Rohde、DerryBerry、David Y. Gin

  DOI：10.1021/ja062364i

  日期：2006.9.1

  QS-21 is one of the most promising new adjuvants for immune response potentiation and dose-sparing in vaccine therapy given its exceedingly high level of potency and its favorable toxicity profile. Melanoma, breast cancer, small cell lung cancer, prostate cancer, HIV-1, and malaria are among the numerous maladies targeted in more than 80 recent and ongoing vaccine therapy clinical trials involving QS-21 as a critical adjuvant component for immune response augmentation. QS-21 is a natural product immunostimulatory adjuvant, eliciting both T-cell- and antibody-mediated immune responses with microgram doses. Herein is reported the synthesis of QS-21A(api) in a highly modular strategy, applying novel glycosylation methodologies to a convergent construction of the potent saponin immunostimulant. The chemical synthesis of QS-21 offers unique opportunities to probe its mode of biological action through the preparation of otherwise unattainable nonnatural saponin analogues.