methyl 7-oxopodocarpa-8,11,13-trien-19-oate | 22489-70-9

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: methyl 7-oxopodocarpa-8,11,13-trien-19-oate
• 英文别名: 7-oxo-podocarpa-8,11,13-trien-16-oic acid methyl ester；7-Oxo-podocarpa-8,11,13-trien-16-saeure-methylester；methyl (1S,4aS,10aR)-1,4a-dimethyl-9-oxo-3,4,10,10a-tetrahydro-2H-phenanthrene-1-carboxylate
• CAS: 22489-70-9
• 化学式: C₁₈H₂₂O₃
• 分子量: 286.371
• InChiKey: VLZCYMUKCICBKI-NXHRZFHOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  21
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.56
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  methyl 7-oxopodocarpa-8,11,13-trien-19-oate 在 selenium(IV) oxide 、 溶剂黄146 作用下， 生成 5,6-Dehydro-7-oxo-desoxy-podocarpsaeure-methylester
  参考文献：
  名称：

  DERIVATIVES OF DEHYDROABIETIC AND PODOCARPIC ACIDS

  摘要：

  本文介绍了芳香树脂酸系列中腈的锂铝氢化还原成醛亚胺的过程，以及产物转化为其他衍生物的方法。注意到腈的立体化学对还原速率的影响。指出了脱氢松香烷转化为脱氢产物的过程。讨论了白杉酸的脱羧-5,6-脱氢-7-酮衍生物及其光学对映体的合成。报道了白杉酸的5,6-脱氢衍生物的氢化立体化学。说明了7-酮基团对芳香树脂酸甲酯水解速率的影响。描绘了甲基白杉酸的6-溴-7-酮衍生物与碱反应的反应过程。

  DOI：

  10.1139/v63-284
• 作为产物：
  描述：

  methyl podocarpate 在 chromium(VI) oxide 、 二乙基亚磷酸氢酯 、 lithium 作用下， 生成 methyl 7-oxopodocarpa-8,11,13-trien-19-oate
  参考文献：
  名称：

  Partial Degradation and Reconstitution of Podocarpic Acid. A Novel Method of Hydrolysis of Highly Sterically Hindered Esters¹

  摘要：

  DOI：

  10.1021/ja01534a055

文献信息

• Acid-Promoted Fries Rearrangements of Benzannulated Lactones
  作者：Richard C. Cambie、Lorna H. Mitchell、Peter S. Rutledge

  DOI：10.1071/c98023

  日期：——

  The scope of acid-promoted Fries rearrangements of benzannulated lactones has been examined. The reaction is applicable to seven-membered lactones possessing a sufficiently activated aromatic ring but not to six-membered lactones, and it proceeds in higher yield for diterpenoid lactones than for lower molecular weight lactones. The structures of the 2,6-methano-bridged benzoxocin side products (23), (24), and (25) from rearrangement of the diterpenoid lactone (11) have been assigned.

  研究了苯并内酯在酸促进下进行弗里斯重排的范围。 进行了研究。该反应适用于具有足够活化芳香环的七元内酯 但不适用于六元内酯。 二萜内酯的产率高于分子量较低的内酯。 二萜内酯的产率高于分子量较低的内酯。2,6-甲桥苯并氧杂环己烷副产品（23,6-甲桥苯并氧杂环己烷）的结构为 2,6-甲桥苯并氧羰基副产物(23)、(24)和(25)的结构。 二萜内酯 (11) 重排生成的 2,6-甲桥苯并恶嗪副产品 (23)、(24) 和 (25) 的结构已经确定。
• Organomanganese complexes of podocarpic acid derivatives
  作者：Richard C. Cambie、Michael R. Metzler、Clifton E.F. Rickard、Peter S. Rutledge、Paul D. Woodgate

  DOI：10.1016/0022-328x(92)80023-q

  日期：1992.2

  Cyclomanganation reactions of podocarpic acid derivatives containing aldehyde, ketone, ester, or oxime groups as directing functionalities have been investigated. Attempted complexation of amide-containing ligands proved generally to be unsuccessful whereas benzylic ketones gave their corresponding tetracarbonyl complexes in high yields. Complexation of ligands containing either two potential sites

  已经研究了包含醛，酮，酯或肟基团作为指导官能团的罗汉果酸衍生物的环锰化反应。尝试证明含酰胺配体的络合通常是不成功的，而苄基酮则以高收率得到了它们相应的四羰基络合物。还研究了包含两个潜在的潜在锰基位点或两个潜在的连接基团的配体的络合，并通过NMR或X射线晶体学明确地确定了分离出的络合物的结构
• Stereoselective synthesis and some reactions of β-(η6-arene)Cr(CO)3 complexes of podocarpic acid derivatives
  作者：George R. Clark、Bianca Kuipers、Michael R. Metzler、Manh H. Nguyen、Paul D. Woodgate

  DOI：10.1016/s0022-328x(97)00220-9

  日期：1997.1

  The stereoselective synthesis of a number of (η6-arene)tricarbonylchromium(0) complexes derived from podocarpic acid has been achieved in good to excellent yield. The stereochemistry of complexes 36 and 37 was established by X-ray crystallography. Reactions of some of the deprotonated complexes with electrophiles were investigated.

  许多的立体选择性合成（η 6 -arene）tricarbonylchromium（0）复合物从罗汉松酸衍生的已取得良好到优异的产率。配合物36和37的立体化学通过X射线晶体学确定。研究了一些去质子配合物与亲电试剂的反应。
• Cyclomanganation of diterpenoids; functionalization of C14
  作者：Richard C. Cambie、Michael R. Metzler、Peter S. Rutledge、Paul D. Woodgate

  DOI：10.1016/0022-328x(90)85462-8

  日期：1990.1

  Orthomanganated complexes have been made from carbonyl derivatives of the ring-C aromatic diterpenoids podocarpic acid and dehydroabietic acid. Activation of these complexes with Me3NO followed by coupling reactions with various substituted alkenes results in efficient substitution at C14. In some cases a tetracyclic indenol derivative is formed directly. Insertion of an alkyne also leads to cyclopentaannulation

  用环-C芳族二萜类罗汉果酸和脱氢松香酸的羰基衍生物制备了正锰配合物。这些配合物用Me 3 NO活化，然后与各种取代的烯烃进行偶联反应，可在C14处进行有效取代。在某些情况下，直接形成四环茚满醇衍生物。炔的插入还导致环戊环化。
• Reactions with alkenes of η2-7-oxotetracarbonylmanganese complexes derived from diterpenoids
  作者：Richard C. Cambie、Michael R. Metzler、Peter S. Rutledge、Paul D. Woodgate

  DOI：10.1016/0022-328x(92)83318-c

  日期：1992.5

  A number of activated 7-oxotetracarbonylmanganese(I) complexes derived from podocarpic acid (1) and from dehydroabietic acid have been coupled with alkenes to give C(14) functionalised derivatives in high yields. Some coupling reactions resulted in cyclization to C(7), forming 4H-acephenanthrylene derivatives in moderate yields. Several modes of activating these manganese complexes towards coupling reactions were investigated; these included oxidative decarbonylation at room temperature, thermal promotion, and palladium-mediation.