(4S,6S)-5,5-dimethylnona-1,8-diene-4,6-diol | 1434077-49-2

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: (4S,6S)-5,5-dimethylnona-1,8-diene-4,6-diol
• CAS: 1434077-49-2
• 化学式: C₁₁H₂₀O₂
• 分子量: 184.279
• InChiKey: QLRPWSGFPOVURF-UWVGGRQHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  13
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.64
• 拓扑面积：
  40.5
• 氢给体数：
  2
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (4S,6S)-5,5-dimethylnona-1,8-diene-4,6-diol 在 2,6-二甲基吡啶 、 4-二甲氨基吡啶 、 sodium tetrahydroborate 、 potassium permanganate 、 sodium periodate 、 L(+)-tartaric acid 、 三乙胺 、 N,N-二异丙基乙胺 、 bromo-tris(1-pyrrolidinyl)phosphonium hexafluorophosphate 、 copper dichloride 、 palladium dichloride 、 lithium hexamethyldisilazane 作用下， 以 四氢呋喃 、 二氯甲烷 、 乙腈 、 叔丁醇 为溶剂， 反应 74.5h， 生成
  参考文献：
  名称：

  Synthesis of seco-B-Ring Bryostatin Analogue WN-1 via C–C Bond-Forming Hydrogenation: Critical Contribution of the B-Ring in Determining Bryostatin-like and Phorbol 12-Myristate 13-Acetate-like Properties

  摘要：

  The seco-B-ring bryostatin analogue, macrodiolide WN-1, was prepared in 17 steps (longest linear sequence) and 30 total steps with three bonds formed via hydrogen-mediated C-C coupling. This synthetic route features a palladium-catalyzed alkoxycarbonylation of a C2-symmetric diol to form the C9-deoxygenated bryostatin A-ring. WN-1 binds to PKCα (Ki = 16.1 nM) and inhibits the growth of multiple leukemia cell lines. Although structural features of the WN-1 A-ring and C-ring are shared by analogues that display bryostatin-like behavior, WN-1 displays PMA-like behavior in U937 cell attachment and proliferation assays, as well as in K562 and MV-4-11 proliferation assays. Molecular modeling studies suggest the pattern of internal hydrogen bonds evident in bryostatin 1 is preserved in WN-1, and that upon docking WN-1 into the crystal structure of the C1b domain of PKCδ, the binding mode of bryostatin 1 is reproduced. The collective data emphasize the critical contribution of the B-ring to the function of the upper portion of the molecule in conferring a bryostatin-like pattern of biological activity.

  DOI：

  10.1021/ja507825s
• 作为产物：
  描述：

  乙酸烯丙酯 、 2,2-二甲基-1,3-丙二醇 在 bis(1,5-cyclooctadiene)diiridium(I) dichloride 、 caesium carbonate 、 R-(+)-1,1'-联萘-2,2'-双二苯膦 、 4-氯-3-硝基苯甲酸 作用下， 以 四氢呋喃 为溶剂， 反应 120.5h， 以40%的产率得到(4S,6S)-5,5-dimethylnona-1,8-diene-4,6-diol
  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

文献信息

• Protecting-Group-Free Diastereoselective CC Coupling of 1,3-Glycols and Allyl Acetate through Site-Selective Primary Alcohol Dehydrogenation
  作者：Anne-Marie R. Dechert-Schmitt、Daniel C. Schmitt、Michael J. Krische

  DOI：10.1002/anie.201209863

  日期：2013.3.11

  Safe from protection! A pronounced kinetic preference for primary alcohol dehydrogenation enables the site‐selective iridium catalyzed CC coupling of polyols with allyl acetate in the absence of protecting groups, premetallated reagents, chiral auxiliaries, and discrete alcohol‐to‐aldehyde oxidation.

  安全无保护！伯醇脱氢的显着动力学偏好使得在没有保护基团、预金属化试剂、手性助剂和离散醇到醛氧化的情况下，位点选择性铱催化多元醇与乙酸烯丙酯的C  C 偶联成为可能。
• 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。
• Synthesis of <i>seco</i>-B-Ring Bryostatin Analogue WN-1 via C–C Bond-Forming Hydrogenation: Critical Contribution of the B-Ring in Determining Bryostatin-like and Phorbol 12-Myristate 13-Acetate-like Properties
  作者：Ian P. Andrews、John M. Ketcham、Peter M. Blumberg、Noemi Kedei、Nancy E. Lewin、Megan L. Peach、Michael J. Krische

  DOI：10.1021/ja507825s

  日期：2014.9.24

  The seco-B-ring bryostatin analogue, macrodiolide WN-1, was prepared in 17 steps (longest linear sequence) and 30 total steps with three bonds formed via hydrogen-mediated C-C coupling. This synthetic route features a palladium-catalyzed alkoxycarbonylation of a C2-symmetric diol to form the C9-deoxygenated bryostatin A-ring. WN-1 binds to PKCα (Ki = 16.1 nM) and inhibits the growth of multiple leukemia cell lines. Although structural features of the WN-1 A-ring and C-ring are shared by analogues that display bryostatin-like behavior, WN-1 displays PMA-like behavior in U937 cell attachment and proliferation assays, as well as in K562 and MV-4-11 proliferation assays. Molecular modeling studies suggest the pattern of internal hydrogen bonds evident in bryostatin 1 is preserved in WN-1, and that upon docking WN-1 into the crystal structure of the C1b domain of PKCδ, the binding mode of bryostatin 1 is reproduced. The collective data emphasize the critical contribution of the B-ring to the function of the upper portion of the molecule in conferring a bryostatin-like pattern of biological activity.