15,16-bis(3-methoxy-3-oxoprop-1-en-1-yl)-15,16-epoxy-8(9),13(16),14-labdatrien-18-oic acid methyl ester | 1311993-13-1

• 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: 15,16-bis(3-methoxy-3-oxoprop-1-en-1-yl)-15,16-epoxy-8(9),13(16),14-labdatrien-18-oic acid methyl ester
• 英文别名: methyl (1S,4aS,8aR)-5-(2-{2,5-bis[(E)-3-methoxy-3-oxoprop-1-en-1-yl]furan-3-yl}ethyl)-1,4a,6-trimethyl-1,2,3,4,4a,7,8,8a-octahydronaphthalene-1-carboxylate；15,16-bis((E)-3-methoxy-3-oxoprop-1-en-1-yl)-15,16-epoxy-8(9),13(16),14-labdatrien-18-oic acid methyl ester；Methyl (1s,4as,8ar)-5-(2-{2,5-bis[(e)-3-methoxy-3-oxoprop-1-en-1-yl]furan-3-yl}ethyl)-1,4a,6-tri-methyl-1,2,3,4,4a,7,8,8a-octahydronaphthalene-1-carboxylate；methyl (1S,4aS,8aR)-5-[2-[2,5-bis[(E)-3-methoxy-3-oxoprop-1-enyl]furan-3-yl]ethyl]-1,4a,6-trimethyl-2,3,4,7,8,8a-hexahydronaphthalene-1-carboxylate
• CAS: 1311993-13-1
• 化学式: C₂₉H₃₈O₇
• 分子量: 498.617
• InChiKey: LKHDZKAQSQUUCA-TYBMSMDRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.3
• 重原子数：
  36
• 可旋转键数：
  11
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.55
• 拓扑面积：
  92
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为产物：
  描述：

  phlomisoic acid methyl ester 、 丙烯酸甲酯（MA） 在 氧气 、 copper diacetate 、 palladium diacetate 、 对苯醌 作用下， 以 丙酸 、 乙腈 为溶剂， 反应 80.0h， 以54%的产率得到16-(3-methoxy-3-oxoprop-1-en-1-yl)-15,16-epoxy-8(9),13(16),14-labdatrien-18-oic acid methyl ester
  参考文献：
  名称：

  Synthetic transformations of higher terpenoids: XXXII. Synthesis of 16-alkenyl-substituted labdatrienes by oxidative coupling of methyl phlomisoate with alkenes

  摘要：

  Reactions of methyl phlomisoate with methyl acrylate, phenyl acrylate, methyl vinyl ketone, phenyl vinyl ketone, or N-substituted acrylamides catalyzed by Pd(OAc)(2) in the presence of Cu(OAc)(2), p-benzoquinone in the mixture of propionic acid and acetonitrile proceed regio- and stereoselectively with the formation of (E)-16-vinyl labdatrienoates. The oxidative coupling under these conditions of the methyl phlomisoate with styrene results in a mixture of 15,16-distyryl-, 16-styryl-, and 16-(1-phenylvinyl)-derivatives of furanolabdanoid.

  DOI：

  10.1134/s1070428013110225

文献信息

• Synthetic transformations of higher terpenoids: XXV. Cross coupling of phlomisoic acid methyl ester with alkenes in the presence of oxidants
  作者：Yu. V. Kharitonov、E. E. Shul’ts、M. M. Shakirov、G. A. Tolstikov

  DOI：10.1134/s107042801104021x

  日期：2011.4

  The reaction of phlomisoic acid methyl ester with styrene, catalyzed by Pd(OAc)(2), in the presence of Cu(OAc)(2) and 1,4-benzoquinone in a mixture of propionic acid with diethyl ether gave the corresponding 15,16-distyryl derivative and only traces of 15- and 16-monosubstituted furanolabdanoids. Oxidative coupling of the title compound with methyl acrylate under analogous conditions afforded a mixture of 15-mono-, 16-mono-, and 15,16-dialkenylation products whose ratio changed during the process. The reaction was stereoselective, and the exocyclic double bond in the products had exclusively E configuration.
• Synthetic transformations of higher terpenoids: XXXII. Synthesis of 16-alkenyl-substituted labdatrienes by oxidative coupling of methyl phlomisoate with alkenes
  作者：Yu. V. Kharitonov、O. I. Kremenko、E. E. Shults、M. M. Shakirov、G. A. Tolstikov

  DOI：10.1134/s1070428013110225

  日期：2013.11

  Reactions of methyl phlomisoate with methyl acrylate, phenyl acrylate, methyl vinyl ketone, phenyl vinyl ketone, or N-substituted acrylamides catalyzed by Pd(OAc)(2) in the presence of Cu(OAc)(2), p-benzoquinone in the mixture of propionic acid and acetonitrile proceed regio- and stereoselectively with the formation of (E)-16-vinyl labdatrienoates. The oxidative coupling under these conditions of the methyl phlomisoate with styrene results in a mixture of 15,16-distyryl-, 16-styryl-, and 16-(1-phenylvinyl)-derivatives of furanolabdanoid.