(+)-Thyrsiferol | 93453-12-4

• 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: (+)-Thyrsiferol
• 英文别名: thyrsiferol；thyrsiferyl；thysiferol；(1S,4S)-4-[(2R,4aS,6R,8aR)-2-[(2S,5R)-5-bromo-2,6,6-trimethyloxan-2-yl]-4a-methyl-3,4,6,7,8,8a-hexahydro-2H-pyrano[3,2-b]pyran-6-yl]-1-[(2R,5R)-5-(2-hydroxypropan-2-yl)-2-methyloxolan-2-yl]pentane-1,4-diol
• CAS: 93453-12-4；105880-10-2；116502-09-1；66873-39-0
• 化学式: C₃₀H₅₃BrO₇
• 分子量: 605.651
• InChiKey: IFHPYSVGNHWKDY-JXHBSGSUSA-N

物化性质

• 熔点：
  104.5-106 (Acetate ester)

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  38
• 可旋转键数：
  7
• 环数：
  4.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  97.6
• 氢给体数：
  3
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  乙酸酐 、 (+)-Thyrsiferol 在 吡啶 作用下， 反应 18.0h， 以70%的产率得到thyrsiferyl 18-acetate
  参考文献：
  名称：

  Total Synthesis of Thyrsiferyl 23-Acetate, a Specific Inhibitor of Protein Phosphatase 2A and an Anti-Leukemic Inducer of Apoptosis

  摘要：

  A convergent synthetic entry to the squalenoid polyether system has been developed and applied to the biologically active marine natural products thyrsiferyl 23-acetate (la), thyrsiferol (Ib), thyrsiferyl 18-acetate (Ic), and thyrsiferyl 18,23-diacetate (Id). This involved the separate construction of two advanced intermediates representing the C1-C15 (4) and C16-C24 (5) domains, followed by their organochromium-mediated coupling, installation of the tertiary alcohol at C15, and manipulation of the C18 and C23 acetate moieties. The C1-C15 (4) intermediate containing the three tetrahydropyranyl rings (A-B-C) was derived from two preconstructed tetrahydropyran-containing units representing the functionalized A (C2-C6) and C (C10-C14) rings (6 and 7, respectively). The bromotetrahydropyranyl A ring was obtained via bromoetherification of the hydroxyalkene 16, which was synthesized from (2R,3R)-epoxy geraniol. The C ring was stereoselectively constructed by acid-catalyzed opening of the hydroxy epoxide 32, derived from D-glutamic acid. Intermediates 6 and 7 were-joined using organochromium conditions, and ketone and hydroxyl functionalities were installed at carbons:7 and 11, respectively. Closure of the B ring was accomplished stereoselectively by formation of species derived from a C7, C11 keto-alcohol and in situ reduction of a tetrahydropyranyl oxonium. The complementary tetrahydrofuran D (C19-C22) ring was obtained from a geraniol-derived tertiary hydroxy alkene (44) via a stereoselective Re(VII)-induced syn-oxidative cyclization. The side chain appended to the D ring was elaborated into trans-alkenyl iodide 5 under Takai reaction conditions. CrCl2-mediated coupling of aldehyde 4 containing the secondary bromide at C3 of the natural products, with iodide 5 bearing acetate moieties at C18 and C23, installed the C15-C16 carbon-carbon bond. The resultant C15 allylic carbinol was converted into an cr,P-saturated ketone, and the final methyl group was added stereoselectively using methylmagnesium bromide. Saponification of the C18 acetate yielded la, whereas cleavage of both C18 and C23 acetates gave the triol Ib. This modular entry into the squalenoid-polyether system may facilitate further evaluation of the antileukemic, apoptosis-inducing, protein serine/threonine phosphatase 2A inhibitory and anti-multidrug resistance activities of the thyrsiferol-derived natural products.

  DOI：

  10.1021/ja000001r
• 作为产物：
  描述：

  (S)-芳樟醇 在 palladium dihydroxide 、 palladium on activated charcoal chromium dichloride 、 三乙基硅烷 、 manganese(IV) oxide 、 三氟甲磺酸三甲基硅酯 、 2,2,4,6-tetrabromocyclohexa-2,5-dienone 、 氢气 、 碳酸氢钠 、 potassium carbonate 、 戴斯-马丁氧化剂 、 nickel dichloride 作用下， 以 四氢呋喃 、 甲醇 、 乙醚 、 硝基甲烷 、 正己烷 、 二氯甲烷 、 二甲基亚砜 、 乙酸乙酯 、 N,N-二甲基甲酰胺 为溶剂， -78.0~20.0 ℃ 、101.33 kPa 条件下， 反应 85.5h， 生成 (+)-Thyrsiferol
  参考文献：
  名称：

  Total Synthesis of Thyrsiferyl 23-Acetate, a Specific Inhibitor of Protein Phosphatase 2A and an Anti-Leukemic Inducer of Apoptosis

  摘要：

  A convergent synthetic entry to the squalenoid polyether system has been developed and applied to the biologically active marine natural products thyrsiferyl 23-acetate (la), thyrsiferol (Ib), thyrsiferyl 18-acetate (Ic), and thyrsiferyl 18,23-diacetate (Id). This involved the separate construction of two advanced intermediates representing the C1-C15 (4) and C16-C24 (5) domains, followed by their organochromium-mediated coupling, installation of the tertiary alcohol at C15, and manipulation of the C18 and C23 acetate moieties. The C1-C15 (4) intermediate containing the three tetrahydropyranyl rings (A-B-C) was derived from two preconstructed tetrahydropyran-containing units representing the functionalized A (C2-C6) and C (C10-C14) rings (6 and 7, respectively). The bromotetrahydropyranyl A ring was obtained via bromoetherification of the hydroxyalkene 16, which was synthesized from (2R,3R)-epoxy geraniol. The C ring was stereoselectively constructed by acid-catalyzed opening of the hydroxy epoxide 32, derived from D-glutamic acid. Intermediates 6 and 7 were-joined using organochromium conditions, and ketone and hydroxyl functionalities were installed at carbons:7 and 11, respectively. Closure of the B ring was accomplished stereoselectively by formation of species derived from a C7, C11 keto-alcohol and in situ reduction of a tetrahydropyranyl oxonium. The complementary tetrahydrofuran D (C19-C22) ring was obtained from a geraniol-derived tertiary hydroxy alkene (44) via a stereoselective Re(VII)-induced syn-oxidative cyclization. The side chain appended to the D ring was elaborated into trans-alkenyl iodide 5 under Takai reaction conditions. CrCl2-mediated coupling of aldehyde 4 containing the secondary bromide at C3 of the natural products, with iodide 5 bearing acetate moieties at C18 and C23, installed the C15-C16 carbon-carbon bond. The resultant C15 allylic carbinol was converted into an cr,P-saturated ketone, and the final methyl group was added stereoselectively using methylmagnesium bromide. Saponification of the C18 acetate yielded la, whereas cleavage of both C18 and C23 acetates gave the triol Ib. This modular entry into the squalenoid-polyether system may facilitate further evaluation of the antileukemic, apoptosis-inducing, protein serine/threonine phosphatase 2A inhibitory and anti-multidrug resistance activities of the thyrsiferol-derived natural products.

  DOI：

  10.1021/ja000001r

文献信息

• Total synthesis of (+)-thyrsiferol and (+)-venustatriol
  作者：Masaru Hashimoto、Toshiyuki Kan、Koji Nozaki、Mitsutoshi Yanagiya、Haruhisa Shirahama、Takeshi Matsumoto

  DOI：10.1016/s0040-4039(00)86672-1

  日期：1988.1

  Triterpenoid polyethers (+)-thyrsiferol (1a) and (+)-venustatriol (1d) were totally synthesized from trivial compounds.

  三萜类聚醚（+）-thyrsiferol（1a）和（+）-venustatriol（1d）由琐碎的化合物完全合成。
• Cytotoxic Squalene-Derived Polyethers from the Marine Red Alga<i>Laurencia obtusa</i>(Hudson) Lamouroux
  作者：Teruaki Suzuki、Satoshi Takeda、Minoru Suzuki、Etsuro Kurosawa、Arata Kato、Yoshihiko Imanaka

  DOI：10.1246/cl.1987.361

  日期：1987.2.5

  Five new cytotoxic triterpenoids with squalene carbon skeleton have been isolated from the title alga. The structures of 15(28)-anhydrothyrsiferyl diacetate, 15-anhydrothyrsiferyl diacetate, and magireol-A were confirmed by the spectral and chemical methods. The structures of magireol-B and -C were deduced from the spectral data.

  已从标题藻类中分离出五种具有角鲨烯碳骨架的新型细胞毒性三萜类化合物。15(28)-脱水thyrsiferyl diacetate、15-anhydrothyrsiferyl diacetate 和magireol-A 的结构通过光谱和化学方法得到证实。从光谱数据推导出magireol-B和-C的结构。
• Total syntheses of (+)-thyrsiferol, (+)-thyrsiferyl 23-acetate, and (+)-venustatriol
  作者：Masaru Hashimoto、Toshiyuki Kan、Koji Nozaki、Mitsutoshi Yanagiya、Haruhisa Shirahama、Takeshi Matsumoto

  DOI：10.1021/jo00304a022

  日期：1990.8
• HASHIMOTO, MASARU;KAN, TOSHIYUKI;NOZAKI, KOJI;YANAGIYA, MITSUTOSHI;SHIRAH+, TETRAHEDRON LETT., 29,(1988) N 10, 1143-1144
  作者：HASHIMOTO, MASARU、KAN, TOSHIYUKI、NOZAKI, KOJI、YANAGIYA, MITSUTOSHI、SHIRAH+

  DOI：——

  日期：——
• AGENTS FOR PREVENTING ATTACHMENT OF BARNACLE CONSISTING OF ORGANIC SOLVENT EXTRACTS OF RED ALGA LAURENCIA SP. AND COMPOUNDS ISOLATED THEREFROM
  申请人：Okino Tatsufumi

  公开号：US20100204315A1

  公开（公告）日：2010-08-12

  An object of the present invention is to provide organic solvent extracts of red algae laurencia sp., compounds isolated and identified therefrom, and an agent for preventing attachment of barnacles comprising them. The present invention relates to a barnacle attachment preventive agent consisting of at least one selected from the group consisting of Laurencin, Thyrsiferol, Magireol A, Omaezallene, Hachijojimallene A and organic solvent extracts of red algae laurencia sp.