(3S,8R)-9-benzyloxy-7-chloroirid-1-ene | 93178-06-4

• 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: (3S,8R)-9-benzyloxy-7-chloroirid-1-ene
• 英文别名: (3S,8R)-9-benzyloxy-7-chloro-1-iridene；[(2R)-2-[(1S)-2-(chloromethyl)-3-methylcyclopent-2-en-1-yl]propoxy]methylbenzene
• CAS: 93178-06-4
• 化学式: C₁₇H₂₃ClO
• 分子量: 278.822
• InChiKey: PNIVHTJFFXOGDU-HOCLYGCPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  19
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.53
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (3S,8R)-9-benzyloxy-7-chloroirid-1-ene 在 palladium dihydroxide 吡啶 、 咪唑 、 六甲基磷酰三胺 、 chromium chloride 、 lithium aluminium tetrahydride 、 氯化亚砜 、 MoO₅*pyridine 、 (COCl₂)2 、 四丁基氟化铵 、 氢气 、 氧气 、 乙酸酐 、 sodium hydride 、 二甲基亚砜 、 乙酰氯 、 lithium hexamethyldisilazane 作用下， 以 N,N-二甲基甲酰胺 、 xylene 为溶剂， 生成 (S)-2-Isopropyl-5-methoxymethoxymethyl-5-[(R)-2-methyl-5-((E)-1-methyl-2-trimethylsilanyloxy-vinyl)-cyclopent-1-enylmethyl]-cyclopenta-1,3-dienecarboxylic acid methyl ester
  参考文献：
  名称：

  Total synthesis of optically active sordaricin methyl ester and its Δ²-derivative

  摘要：

  通过分子内 DielsâAlder 反应，首次合成了具有光学活性的沙苑子苷甲酯及其 A2 衍生物，其适当的前体来自鸢尾苷合成物的二聚缩合物。

  DOI：

  10.1039/c39930001002

文献信息

• Total Synthesis of Dictymal, a B-seco-Dictymenoid Aldehyde from an Alga,<i>Diatyota diohotoma</i>
  作者：Nobuo Kato、Shinya Tanaka、Hideo Kataoka、Hitoshi Takeshita

  DOI：10.1246/cl.1987.2295

  日期：1987.12.5

  A B-seco-dictymenoid aldehyde, dictymal, was synthesized from two optically active iridoid synthons; the required ring system was constructed by lactol-regulated Cope rearrangement and stereoselective Li-tert-BuOH-in-HMPA reduction of the tetrasubstituted C=C.

  B-seco-dictymenoid 醛, dictymal, 是由两个旋光环烯醚合成子合成的；所需的环系统是通过乳醇调节的 Cope 重排和立体选择性 Li-tert-BuOH-in-HMPA 还原四取代 C=C 构建的。
• SYNTHESIS OF FUSICOCCA-2,8,10-TRIENE, A BIOGENETIC MISSING LINK, STARTING FROM STEREOSPECIFIC CONDENSATION OF TWO IRIDOID SYNTHONS
  作者：Hitoshi Takeshita、Nobuo Kato、Kohji Nakanishi、Hirotaka Tagoshi、Toshihide Hatsui

  DOI：10.1246/cl.1984.1495

  日期：1984.9.5

  From two units of iridoid C10-synthons which could be prepared from one of the photoadducts of isoprene and methyl 2,4-dioxopentanoate, the hydrocarbon which can be designated as fusicocca-2,8,10-triene, a missing link in the biogenesis, was stereospecifally synthesized.

  来自两个单元的环烯醚萜 C10-合成子，可以从异戊二烯和 2,4-二氧代戊酸甲酯的光加合物之一制备，碳氢化合物可以被指定为 fusicocca-2,8,10-triene，生物发生中的一个缺失环节, 是立体特异性合成的。
• Synthetic Photochemistry. XLII. Total Synthesis of Cycloaraneosene, a Fundamental Hydrocarbon of 5–8–5-Membered Tricydic Diterpenoid from<i>Sordaria araneosa</i>
  作者：Nobuo Kato、Shinya Tanaka、Hitoshi Takeshita

  DOI：10.1246/bcsj.61.3231

  日期：1988.9

  A 5–8–5-membered tricyclic diterpene, cycloaraneosene, has been totally synthesized via a stereoselective condensation of two units of optically active iridoids, a Cope rearrangement, a chemical reduction of the tetrasubstituted double bond, and the formation of an eight-membered ring. The proposed structure of natural hydroxycycloaraneosene should be revised to 8β-hydroxycycloaraneosene, judging from the NMR spectral data.

  通过立体选择性缩合两个单元的光学活性虹彩、科普重排、四取代双键的化学还原以及八元环的形成，完全合成了一种 5-8-5 元三环二萜--环胂烯。从核磁共振光谱数据来看，拟议的天然羟基环戊烯的结构应修改为 8β-羟基环戊烯。
• Total Synthesis of Cycloaraneosene, a Fundamental Hydrocarbon of “epi”-Fusicoccane Diterpenoids, and the Structure Revision of Its Congener, Hydroxycycloaraneosene
  作者：Nobuo Kato、Shinya Tanaka、Hitoshi Takeshita

  DOI：10.1246/cl.1986.1989

  日期：1986.11.5

  The 5-8-5-membered tricyclic diterpene, cycloaraneosene, has been totally synthesized via the stereoselective condensation of two units of optically active iridoids, Cope rearrangement and chemical reduction of the tetrasubstituted C=C bond. The NMR spectrum of synthetic 9α-hydroxycycloaraneosene was not identical with the congener product, and the natural alcohol is likely to be 8β-hydroxyl derivative.

  通过立体选择性缩合两个单元的光学活性虹彩、科普重排和四取代 C=C 键的化学还原，完全合成了 5-8-5 元三环二萜环胂烯。合成的 9α-hydroxycycloaraneosene 的核磁共振谱与同系物不完全相同，天然醇可能是 8β-hydroxyl 衍生物。
• Total synthesis of albolic acid and ceroplastol II, 5–8–5-membered tricyclic insect sesterterpenoids, via a lactol-regulated silyloxy–Cope rearrangement
  作者：Nobuo Kato、Hideo Kataoka、Shoji Ohbuchi、Shinya Tanaka、Hitoshi Takeshita

  DOI：10.1039/c39880000354

  日期：——

  Optically active albolic acid and ceroplastol II, 5–8–5-membered tricyclic sesterterpenoids, were stereoselectively synthesised from two C10 synthons (iridoids)via CrCl2-condensation, lactol-regulated silyloxy–Cope rearrangement with a normally disfavoured boat transition geometry, TiCl2-ring closure, and C5-homologation.

  光学活性的阿尔贝酸和5 －8－元三环酯基萜烯类化合物，是通过CrCl 2-缩合，乳醇调节的甲硅烷氧基-Cope重排与两个C 10合成子（类铱）立体选择性合成的，且通常具有船体过渡几何构型， TiCl 2环封闭，C 5均一。