methyl 3-oxo-11βH-eudesma-1,4,6-trien-12-oate | 57901-34-5

• 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 3-oxo-11βH-eudesma-1,4,6-trien-12-oate
• 英文别名: methyl (2S)-2-[(4aS)-4a,8-dimethyl-7-oxo-3,4-dihydronaphthalen-2-yl]propanoate
• CAS: 57901-34-5
• 化学式: C₁₆H₂₀O₃
• 分子量: 260.333
• InChiKey: CLYRAVPNXDHNJP-QFYYESIMSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  19
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.5
• 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 3-oxo-11βH-eudesma-1,4,6-trien-12-oate 在 palladium on activated charcoal selenium(IV) oxide 、 氢气 、 对甲苯磺酸 作用下， 以 1,4-二氧六环 为溶剂， 反应 7.0h， 生成 3-oxo-4,7,11αH,5,8βH-eudesman-8,12-olide
  参考文献：
  名称：

  Functionality transfer from C6 to C8 in sesquiterpenes. Synthesis of 8-epi-ivangustin and 8-epi-isoivangustin from santonin

  摘要：

  The short-range functionality transfer from C6 to C8 in eudesmane framework was reported. Santonin (1) was converted into 8-epi-ivangustin (16) and 8-epi-isoivangustin (18) via a synthetic pathway involving the aforementioned functionality transfer and treatment of an intermediate diselenide 9 with m-CPBA.

  DOI：

  10.1021/jo00021a040
• 作为产物：
  描述：

  山道年 在 吡啶 、 sodium hydroxide 、 氯化亚砜 作用下， 以 乙醇 、 水 、 N,N-二甲基甲酰胺 为溶剂， 反应 1.75h， 生成 methyl 3-oxo-11βH-eudesma-1,4,6-trien-12-oate
  参考文献：
  名称：

  Functionality transfer from C6 to C8 in sesquiterpenes. Synthesis of 8-epi-ivangustin and 8-epi-isoivangustin from santonin

  摘要：

  The short-range functionality transfer from C6 to C8 in eudesmane framework was reported. Santonin (1) was converted into 8-epi-ivangustin (16) and 8-epi-isoivangustin (18) via a synthetic pathway involving the aforementioned functionality transfer and treatment of an intermediate diselenide 9 with m-CPBA.

  DOI：

  10.1021/jo00021a040

文献信息

• Studies on the terpenoids and related alicyclic compounds. XXVIII. Chemical transformations of .ALPHA.-santonin into C-8 lactonized eudesmanolides: Yomogin and diastereoisomers of dihydrograveolide.
  作者：KOJI YAMAKAWA、KIYOSHI NISHITANI、AKIHIRO MURAKAMI、AKIHIRO YAMAMOTO

  DOI：10.1248/cpb.31.3397

  日期：——

  The chemical transformations of α-santonin (1), a C-6 lactonized eudesmanolide, into C-8 lactonized eudesmanolides, i.e., yomogin (2) and four diastereoisomers of dihydrograveolide (36-39), are described. Transposition of 6, 13-olide into 8, 13-olide in eudesmanolides was investigated. Allylic oxidation of the trienone (12) with tert-butyl chromate gave 3, 8-dioxotriene (20) and 3, 6-dioxotriene (22). Reductive lactonization of 20 gave 11α- and 11β-methyl cis-lactones (30 and 31). Yomogin (2) was synthesized from the cis-lactones (32 and 33) by phenylselenenylation and deselenoxylation procedures. Catalytic reduction of 30 and 31 gave diastereoisomers of dihydrograveolide (36-39).

  α-山道年（1）是一种C-6内酯化的桉叶烷内酯，本文描述了其转化为C-8内酯化的桉叶烷内酯，即扁蒿素（2）和二氢墓亭内酯（36-39）的四种立体异构体的过程。研究了桉叶烷内酯中6,13-内酯向8,13-内酯的转移。三烯酮（12）与叔丁基铬酸酯的烯丙位氧化得到3,8-二氧三烯（20）和3,6-二氧三烯（22）。20的部分还原内酯化得到11α-和11β-甲基顺式内酯（30和31）。通过苯基硒化和去硒氧化的方法，从顺式内酯（32和33）合成了扁蒿素（2）。30和31的催化还原得到二氢墓亭内酯（36-39）的立体异构体。
• Unprecedented sesterterpenoids, orientanoids A–C: discovery, bioinspired total synthesis and antitumor immunity
  作者：Cheng-Yu Zheng、Jin-Xin Zhao、Chang-Hao Yuan、Xia Peng、Meiyu Geng、Jing Ai、Yao-Yue Fan、Jian-Min Yue

  DOI：10.1039/d3sc04238c

  日期：——

  Sesterterpenoids are a very rare class of important natural products. Three new skeletal spiro sesterterpenoids, named orientanoids A–C (1–3), were isolated from Hedyosmum orientale. Their structures were determined by a combination of spectroscopic data, X-ray crystallography, and total synthesis. To obtain adequate materials for biological research, the bioinspired total syntheses of 1–3 were effectively

  二倍萜类化合物是一类非常罕见的重要天然产物。从Hedyosmum orienTAle中分离出三种新的骨架螺二倍萜类化合物，命名为 orienTAnoids A–C ( 1–3 )。它们的结构是通过光谱数据、X 射线晶体学和全合成的结合来确定的。为了获得足够的生物学研究材料，在不使用任何保护基团的情况下，从市售三通宁中，通过7-8步有效地实现了1-3的仿生全合成，总产率为2.3-6.4%。此外，本工作还将红豆素B( 6 )和C( 10 )的立体化学修改为11R-构型。肿瘤相关巨噬细胞（TAM）已成为癌症治疗中的重要治疗靶点。深入的生物学评估表明，这些二倍萜类化合物在体外拮抗巨噬细胞的促肿瘤和免疫抑制功能表型。其中，最有效和最重要的化合物1抑制促肿瘤M2样巨噬细胞并激活细胞毒性CD8 + T细胞，从而抑制体内肿瘤生长。
• Synthesis of two natural 8-oxo-β-cyperone derivatives from (−)-santonin.
  作者：Luz Cardona、Begoña García、Cristina L. García、José R. Pedro

  DOI：10.1016/s0040-4020(01)87256-2

  日期：1993.8

  This paper reports on the chemical transformations of (-)-santonin into (+)-8-oxo-beta-cyperone and (+)-12-hydroxy-8-oxo-beta-cyperone involving 8-oxo group introduction and elaboration of the side chain.