2-((2S,4S,6R)-6-((R)-2-hydroxybutyl)-3,3-dimethyl-4-(((2S,3R,4S,5R)-3,4,5-trimethoxytetrahydro-2H-pyran-2-yl)oxy)tetrahydro-2H-pyran-2-yl)acetic acid

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2-((2S,4S,6R)-6-((R)-2-hydroxybutyl)-3,3-dimethyl-4-(((2S,3R,4S,5R)-3,4,5-trimethoxytetrahydro-2H-pyran-2-yl)oxy)tetrahydro-2H-pyran-2-yl)acetic acid
• 英文别名: 2-[(2S,4S,6R)-6-[(2R)-2-hydroxybutyl]-3,3-dimethyl-4-[(2S,3R,4S,5R)-3,4,5-trimethoxyoxan-2-yl]oxyoxan-2-yl]acetic acid
• 化学式: C₂₁H₃₈O₉
• 分子量: 434.527
• InChiKey: SRAWVPGTVVXJSC-FCOMTRKTSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 重原子数：
  30
• 可旋转键数：
  10
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.95
• 拓扑面积：
  113
• 氢给体数：
  2
• 氢受体数：
  9

反应信息

• 作为反应物：
  描述：

  2-((2S,4S,6R)-6-((R)-2-hydroxybutyl)-3,3-dimethyl-4-(((2S,3R,4S,5R)-3,4,5-trimethoxytetrahydro-2H-pyran-2-yl)oxy)tetrahydro-2H-pyran-2-yl)acetic acid 在 4-二甲氨基吡啶 、 2-甲基-6-硝基苯甲酸酐 作用下， 以 甲苯 为溶剂， 以60%的产率得到cyanolide A
  参考文献：
  名称：

  在没有保护基团、手性助剂或预金属化碳亲核试剂的情况下全合成氰化物 A

  摘要：

  没有保护，没问题：C 2对称大二环内酯氰化物 A 是由新戊二醇和乙酸烯丙酯通过铱催化的双不对称烯丙基化和串联交叉复分解/氧杂-迈克尔环化反应形成取代的吡喃，分六步制备的。该合成是在没有任何保护基团、手性助剂或预金属化碳亲核试剂的情况下完成的，步骤少于任何现有方法的一半。

  DOI：

  10.1002/anie.201300843
• 作为产物：
  描述：

  (R)-1-((2R,4S,6S)-6-(2-hydroxyethyl)-5,5-dimethyl-4-(((2S,3R,4S,5R)-3,4,5-trimethoxytetrahydro-2H-pyran-2-yl)oxy)tetrahydro-2H-pyran-2-yl)butan-2-ol 在 2,2,6,6-四甲基哌啶氧化物 、 碘苯二乙酸 作用下， 以 二氯甲烷 为溶剂， 反应 3.0h， 生成 2-((2S,4S,6R)-6-((R)-2-hydroxybutyl)-3,3-dimethyl-4-(((2S,3R,4S,5R)-3,4,5-trimethoxytetrahydro-2H-pyran-2-yl)oxy)tetrahydro-2H-pyran-2-yl)acetic acid
  参考文献：
  名称：

  Formation of Highly Substituted Tetrahydropyranones: Application to the Total Synthesis of Cyanolide A

  摘要：

  A new tetrahydropyranone synthesis has been developed that leads to cis-2,6-disubstituted 3,3-dimethyltetrahydropyran-4-one rings by condensation of an aldehyde and a hydroxy silyl enol ether. The reaction works with a variety of aldehydes to produce the tetrahydropyranone products in moderate to high yields. This new method was applied to the enantioselective synthesis of cyanolide A and its aglycone.

  DOI：

  10.1021/ol402095g

文献信息

• Total Synthesis of Cyanolide A in the Absence of Protecting Groups, Chiral Auxiliaries, or Premetalated Carbon Nucleophiles
  作者：Andrew R. Waldeck、Michael J. Krische

  DOI：10.1002/anie.201300843

  日期：2013.4.15

  problem: The C2‐symmetric macrodiolide cyanolide A is prepared in six steps from neopentyl glycol and allyl acetate by iridium‐catalyzed double asymmetric allylation and a tandem cross‐metathesis/oxa‐Michael cyclization to form the substituted pyran. The synthesis is accomplished in the absence of any protecting groups, chiral auxiliaries, or premetalated carbon nucleophiles in fewer than half the steps of

  没有保护，没问题：C 2对称大二环内酯氰化物 A 是由新戊二醇和乙酸烯丙酯通过铱催化的双不对称烯丙基化和串联交叉复分解/氧杂-迈克尔环化反应形成取代的吡喃，分六步制备的。该合成是在没有任何保护基团、手性助剂或预金属化碳亲核试剂的情况下完成的，步骤少于任何现有方法的一半。
• Total Synthesis of Cyanolide A and Confirmation of Its Absolute Configuration
  作者：Hyoungsu Kim、Jiyong Hong

  DOI：10.1021/ol101022z

  日期：2010.6.18

  The tandem allylic oxidation/oxa-Michael reaction promoted by the gem-disubstituent effect and the 2-methyl-6-nitrobenzoic anhydride (MNBA)-mediated dimerization were explored for the efficient and facile synthesis of cyanolide A.
• A Synthesis of Cyanolide A by Intramolecular Oxa-Michael Addition
  作者：Roderick Bates、Tee Lek

  DOI：10.1055/s-0033-1341153

  日期：——

  A synthesis of cyanolide A, a diolide natural product, has been achieved using a diastereoselective Barbier reaction, early-stage glycosylation, and intramolecular oxa-Michael addition to form the THP ring.
• Formation of Highly Substituted Tetrahydropyranones: Application to the Total Synthesis of Cyanolide A
  作者：Gidget C. Tay、Michael R. Gesinski、Scott D. Rychnovsky

  DOI：10.1021/ol402095g

  日期：2013.9.6

  A new tetrahydropyranone synthesis has been developed that leads to cis-2,6-disubstituted 3,3-dimethyltetrahydropyran-4-one rings by condensation of an aldehyde and a hydroxy silyl enol ether. The reaction works with a variety of aldehydes to produce the tetrahydropyranone products in moderate to high yields. This new method was applied to the enantioselective synthesis of cyanolide A and its aglycone.