16-formylphlomisoic acid methyl ester | 1276033-61-4

• 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: 16-formylphlomisoic acid methyl ester
• 英文别名: Methyl (1s,4as,8ar)-5-[2-(2-formylfuran-3-yl)-ethyl]-1,4a,6-trimethyl-1,2,3,4,4a,7,8,8a-octahydro-naphthalene-1-carboxylate；methyl (1S,4aS,8aR)-5-[2-(2-formylfuran-3-yl)ethyl]-1,4a,6-trimethyl-2,3,4,7,8,8a-hexahydronaphthalene-1-carboxylate
• CAS: 1276033-61-4
• 化学式: C₂₂H₃₀O₄
• 分子量: 358.478
• InChiKey: ZXTGCBYJCHRIPJ-FCEUIQTBSA-N

物化性质

• 沸点：
  458.2±45.0 °C(Predicted)
• 密度：
  1.082±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.5
• 重原子数：
  26
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.64
• 拓扑面积：
  56.5
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  16-formylphlomisoic acid methyl ester 在 三乙胺 、 sodium hydroxide 、 zinc(II) chloride 作用下， 以 水 、 乙腈 为溶剂， 反应 10.0h， 生成 methyl (1S,4aS,8aR)-5-(2-{2-[(E)-2-ethoxycarbonyl-3-oxobut-1-en-1-yl]furan-3-yl}ethyl)-1,4a,6-trimethylsiloxy-1,2,3,4,4a,7,8,8a-octahydronaphthalene-1-carboxylate
  参考文献：
  名称：

  Synthetic transformations of higher terpenoids: XXVIII. Diels-Alder reactions of 16-(trimethylsiloxybutadienyl) labdanoids

  摘要：

  15,16-Epoxy-16-(3-trimethylsiloxybuta-1,3-dien-1-yl)labdanoids were synthesized, and their reactions with cyclic dienophiles (1,4-benzoquinone, 1,4-toluquinone, 2-bromo-6-methyl-1,4-benzoquinone, and N-methylmaleimide) were studied. The reactions with unsymmetrically substituted benzoquinones were not selective. Methods for the preparation of hybrid compounds containing furan diterpenoid and substituted naphthoquinone, octahydroisoindoletrione, or hexahydroisoindoledione fragments were proposed.

  DOI：

  10.1134/s1070428012060164

文献信息

• Synthesis and spectroscopic studies of furan-bridged polyazamacrocycles through 15,16-bis((prop-2-ynylamino)methyl)labdatriene transformations
  作者：Olga I. Brusentzeva、Yurii V. Kharitonov、Dmitry S. Fadeev、Elvira E. Shults

  DOI：10.1007/s10847-019-00965-z

  日期：2020.4

  Abstract The design and the preparation of a small library of optically active polyazamacrocyclic compounds with a furan bridge, connected by (4-(methylaminomethyl)-1,2,3-triazole) rings with methylene, ethyloxyethyl or ethylethoxyethyl units from natural labdanoid lambertianic acid is reported. The synthesis of the key 15,16-bis((tert-butoxycarbonyl(prop-2-ynyl)amino)methyl)labda-8(9),13,15-labdatriene

  摘要 设计和制备了一个带有呋喃桥的旋光多氮杂大环化合物的小型文库，由（4-（甲基氨基甲基）-1,2,3-三唑）环与来自天然劳丹酸兰伯泰酸的亚甲基、乙氧基乙基或乙基乙氧基乙基单元连接。被报道。还描述了从植物二萜朗伯酸合成关键的 15,16-双（（叔丁氧基羰基（丙-2-炔基）氨基）甲基）labda-8(9),13,15-labdatriene。在二氯甲烷/水反应介质中，在 Cu(II)/抗坏血酸钠的存在下，该化合物与各种二叠氮化物的 CuAAC 反应产生了上述手性大环化合物，其具有结合溶液中 Zn 2+ 离子的呋喃桥。图形摘要
• Synthesis and Analgesic Activity Assessment of Furanolabdanoid Conjugates with Glucuronic Acid
  作者：O. I. Brusentseva、Yu. V. Kharitonov、M. P. Dolgikh、T. G. Tolstikova、E. E. Shul’ts

  DOI：10.1007/s10600-020-03119-7

  日期：2020.7

  Phlomisoic acid reacted with methyl-1-deoxy-2,3,4-tri-O-acetyl-1-bromo-α-D-glucopyranuronate to form the 18-O-β-D-(glucuronopyranoside)-6′-O-methyl ester of 15,16-epoxylabda-8(9),13,14-triene. Reductive amination of methyl 16-formyl-15,16-epoxylabda-8(9),13,14-trienoate or this β-D-glucuronopyranoside of 16-formyl-15,16-epoxylabda-8(9),13,14-triene by propargylamine in the presence of NaBH4 gave the corresponding 16-propargylaminomethyl-15,16-epoxylabda-8(9),13,14-trienes. Copper-catalyzed azide-alkyne cycloaddition of the new terpenoid alkynes and the propargylamide of phlomisoic acid with methyl 1-deoxy-2,3,4-tri-O-acetyl-1-azido-α-D-glucopyranuronate synthesized the corresponding labdanoid glucuronides and diglucuronide. Selective screening of the labdanoid triazolylglucuronides identified compounds with analgesic activity in chemical and thermal irritation tests.

  苯甲异酸与 1-脱氧-2,3,4-O-三乙酰基-1-溴-α-D-吡喃葡萄糖醛酸甲酯反应，生成 15,16-环氧基赖百当-8(9),13,14-三烯的 18-O-β-D-（吡喃葡萄糖醛酸）-6′-O-甲基酯。在 NaBH4 的存在下，丙炔胺对 16-甲酰基-15,16-环氧基赖百当-8(9),13,14-三烯酸甲酯或 16-甲酰基-15,16-环氧基赖百当-8(9),13,14-三烯的β-D-吡喃葡萄糖苷进行还原胺化反应，可得到相应的 16-丙炔胺甲基-15,16-环氧基赖百当-8(9),13,14-三烯。在铜催化下，新的萜类炔烃和 phlomisoic acid 的丙炔酰胺与 1-脱氧-2,3,4-三-O-乙酰基-1-叠氮-α-D-吡喃葡萄糖醛酸甲酯发生叠氮-炔烃环加成反应，合成了相应的唇形酮类葡萄糖醛酸内酯和二葡萄糖醛酸内酯。对拉巴旦类三唑基葡糖苷酸进行选择性筛选，发现了在化学和热刺激试验中具有镇痛活性的化合物。
• Synthetic transformations of higher terpenoids: XXXVI. Synthesis of furanolabdanoid glycoconjugates with a 1,2,3-triazole linker
  作者：O. I. Kremenko、Yu. V. Kharitonov、E. E. Shul’ts

  DOI：10.1134/s1070428017010079

  日期：2017.1

  Procedures have been developed for the synthesis of 16-[(propargyloxy) methyl]- and 7- and 18-(propargyloxy) labda-8(9), 13,14-trienes from phlomisoic acid. Copper-catalyzed cycloaddition of the labdanoid alkynes to azido derivatives of alpha-D-glucose, D-galactose, D-xylose, and L-arabinose afforded the corresponding N-glycosyl-1,2,3- triazole conjugates.