(2Z,4E,8E,12E)-2-(1-Methylethyl)-5,9,13-trimethyl-2,4,8,12-cyclotetradecatetraen-1-one | 77394-15-1

• 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: (2Z,4E,8E,12E)-2-(1-Methylethyl)-5,9,13-trimethyl-2,4,8,12-cyclotetradecatetraen-1-one
• 英文别名: (2Z,4E,8E,12E)-5,9,13-trimethyl-2-propan-2-ylcyclotetradeca-2,4,8,12-tetraen-1-one
• CAS: 77394-15-1
• 化学式: C₂₀H₃₀O
• 分子量: 286.458
• InChiKey: IXLSHNRLPYQCKH-FFZBFBDNSA-N

物化性质

• 沸点：
  412.1±45.0 °C(Predicted)
• 密度：
  0.889±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.7
• 重原子数：
  21
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.55
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (2Z,4E,8E,12E)-2-(1-Methylethyl)-5,9,13-trimethyl-2,4,8,12-cyclotetradecatetraen-1-one 在 lithium aluminium tetrahydride 作用下， 以78%的产率得到(+/-)-sarcophytol A
  参考文献：
  名称：

  Enolate reactions on macrocyclic ring systems. Total synthesis of (.+-.)-sarcophytol A.

  摘要：

  The stereoselective synthesis of (+/-)-sarcophytol A and a discussion of the stereoselectivity in the beta-elimination of alkoxy group of the macrocyclic enolate based on MM2 calculations are presented.

  DOI：

  10.1021/jo00039a002
• 作为产物：
  描述：

  2-(二乙氧基次膦酰基)-3-甲基丁酸乙酯 在 叔丁基过氧化氢 、 正丁基锂 、 selenium(IV) oxide 、 barium permanganate 、 四丁基氟化铵 、 二异丁基氢化铝 、 水杨酸 作用下， 以 四氢呋喃 、 二氯甲烷 、 水 、 甲苯 为溶剂， 反应 92.0h， 生成 (2Z,4E,8E,12E)-2-(1-Methylethyl)-5,9,13-trimethyl-2,4,8,12-cyclotetradecatetraen-1-one
  参考文献：
  名称：

  Total Synthesis of Sarcophytol A, an Anticarcinogenic Marine Cembranoid

  摘要：

  A highly stereo- and enantioselective total synthesis of sarcophytol A (1), a marine cembranoid promising as a cancer chemopreventive agent, is described. The nitrile 10 obtained Z-selectively (Z:E = >35:1) by the Horner-Emmons reaction of (E,E)-farnesal (5) with the phosphononitrile 9 in 91% yield was converted to the conjugated 2(Z),4(E)-dienal 3 in which the terminal (E)-methyl group was functionalized. Intramolecular alkylation of the cyanohydrin TMS ether of 3 provided the macrocyclic ketone 2 in 79% of overall yield from 3 without isolation of the cyclic cyanohydrin 20 as well as its TMS ether 19. Reduction of 2 with several chiral LiAlH4 reagents afforded 1 highly enantioselectively (87-93% ee) in 78-97% yield, from which enantiomerically pure 1 (>99% ee) was readily obtained upon a single recrystallization.

  DOI：

  10.1021/jo00089a011

文献信息

• Marine terpenes and terpenoids. V. Oxidation of sarcophytol A, a potent anti-tumor-promoter from the soft coral sarcophyton glaucum.
  作者：MASARU KOBAYASHI、KAZUHIKO KONDO、KATSUNORI OSABE、HIROSHI MITSUHASHI

  DOI：10.1248/cpb.36.2331

  日期：——

  Sarcophytol A (1a), a potent anti-tumor-promotor cembranoid from the soft coral Sarcophyton glaucum, was subjected to various oxidation reactions. m-Chloroperbenzoic acid oxidation of 1a gave two epoxides (2a, 2b) which were converted to the corresponding diols 6b, 11b, 12b, 12'b and triols 4b, 9b. Lithium aluminum deuteride reduction of 2a gave a C-7 monodeuterated diol; this was used as a model experiment for the tritiation of 1a. Chromic acid oxidation of 1a gave seco-cembranoids 13b-18, a dienone 19, and a dihydrofuran derivative 20a. Sarcophytol A acetate (1b) was less reactive in chromic acid oxidation and afforded a seco-aldehyde 22a and a dihydroxy derivative 23a in low yield. Hydrolysis of 22a followed by acid treatment afforded the furan 18. Hydrolysis of 23a gave a triol, which, on further oxidation, gave the aldehyde 16, the major product of the chromic acid oxidation of 1a.

  1a 的间氯过苯甲酸氧化反应产生了两个环氧化物（2a、2b），并转化为相应的二醇 6b、11b、12b、12'b 和三醇 4b、9b。氘化铝锂还原 2a 后得到 C-7 单氘化二元醇；这被用作 1a 三氘化的模型实验。铬酸氧化 1a 得到仲碳酸酯 13b-18、二烯酮 19 和二氢呋喃衍生物 20a。Sarcophytol A 乙酸酯（1b）在铬酸氧化中的反应性较低，可得到仲醛 22a 和二羟基衍生物 23a，但产量较低。水解 22a 并进行酸处理后可得到呋喃 18。水解 23a 得到三醇，进一步氧化后得到醛 16，这是 1a 的铬酸氧化反应的主要产物。
• Marine terpenes and terpenoids. II. Structures of three cembrane-type diterpenes, sarcophytol-C, sarcophytol-D, and sarcophytol-E, from the soft coral, Sarcophyton glaucun Q. et G.
  作者：TAKASHI NAKAGAWA、MASARU KOBAYASHI、KOJI HAYASHI、HIROSHI MITSUHASHI

  DOI：10.1248/cpb.29.82

  日期：——

  Three new minor cembrane-type diterpenes, sarcophytol-C, sarcophytol-D, and sarcophytol-E, were isolated from the lipid extract of the soft coral, Sarcophyton glaucum Q. et G., collected in southern Japan. Their structures were characterized on the basis of spectral evidence and degradative studies by ozonolysis.

  从日本南部采集的软珊瑚 Sarcophyton glaucum Q. et G.的脂质提取物中分离出了三种新的次要钙膜型二萜类化合物：sarcophytol-C、sarcophytol-D 和 sarcophytol-E。根据光谱证据和臭氧分解的降解研究，确定了它们的结构特征。
• Stereo- and enantioselective total synthesis of sarcophytol-A
  作者：Hisao Takayanagi、Yasunori Kitano、Yasuhiro Morinaka

  DOI：10.1016/s0040-4039(00)89053-x

  日期：1990.1
• TAKAYANAGI, HISAO;KITANO, YASUNORI;MORINAKA, YASUHIRO, TETRAHEDRON LETT., 31,(1990) N3, C. 3317-3320
  作者：TAKAYANAGI, HISAO、KITANO, YASUNORI、MORINAKA, YASUHIRO

  DOI：——

  日期：——
• KOBAYASHI, MASARU;KONDO, KAZUHIKO;OSABE, KATSUNORI;MITSUHASHI, HIROSHI, CHEM. AND PHARM. BULL., 36,(1988) N 7, C. 2331-2341
  作者：KOBAYASHI, MASARU、KONDO, KAZUHIKO、OSABE, KATSUNORI、MITSUHASHI, HIROSHI

  DOI：——

  日期：——