stemodinone | 41943-80-0

• 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: stemodinone
• 英文别名: (1R,2S,7S,10S,12S,13S)-13-hydroxy-2,6,6,13-tetramethyltetracyclo[10.3.1.01,10.02,7]hexadecan-4-one
• CAS: 41943-80-0
• 化学式: C₂₀H₃₂O₂
• 分子量: 304.473
• InChiKey: MTHCEQRYJNYWKN-BVJMBNRTSA-N

物化性质

• 熔点：
  209-210 °C(Solv: ethyl acetate (141-78-6))
• 沸点：
  414.7±38.0 °C(Predicted)
• 密度：
  1.08±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  22
• 可旋转键数：
  0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.95
• 拓扑面积：
  37.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  stemodinone 在 sodium tetrahydroborate 作用下， 以 甲醇 为溶剂， 反应 0.25h， 以0.20 g的产率得到2β,13(S)-dihydroxystemodane
  参考文献：
  名称：

  Investigation of the importance of the C-2 oxygen function in the transformation of stemodin analogues by Rhizopus oryzae ATCC 11145

  摘要：

  A new stemodinoside, stemodin-a-L-arabinofuranoside (5), was isolated from the plant Stemodia maritima. Incubation of stemodin (2) with Rhizopus oryzae ATCC 11145 gave 2alpha,7beta,13(S)-trihydroxystemodane (17) and 2alpha,3beta,13(S),16alpha-tetrahydroxystemodane (18) whilst stemodinone (8) afforded 6alpha,13(S)-dihydroxystemodan-2-one (19). The bioconversion of 2beta,13(S)-dihydroxystemodane (10) by the fungus yielded 2beta,7beta,13(S)-trihydroxystemodane (20) whereas stemod-12-en-2-one (9) provided 7beta,17-dihydroxystemod-12-en-2-one (21). The results provide useful information about the relationship between the functional groups of the substrates and their potential for bioconversion. (C) 2004 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.phytochem.2004.01.011
• 作为产物：
  描述：

  stemodin 在 jones reagent 作用下， 以 丙酮 为溶剂， 反应 0.5h， 以996 mg的产率得到stemodinone
  参考文献：
  名称：

  白僵菌 ATCC 7159 对二萜和二萜衍生物的生物转化

  摘要：

  白僵菌 ATCC 7159 对大黄素和大黄酮的生物羟基化分别产生了 2alpha,13,18-trihydroxystemodane 和 13,18-dihydroxystemodan-2-one。Stemarin 被转换为新型 1beta,13,19-trihydroxystemarane 和 13-hydroxystemarane-19-carb 酸。还研究了大黄素的各种衍生物的合成和生物转化。

  DOI：

  10.1016/s0031-9422(00)00403-9

文献信息

• Bioconversion of Stemodia maritima diterpenes and derivatives by Cunninghamella echinulata var. elegans and Phanerochaete chrysosporium
  作者：A LAMM、W REYNOLDS、P REESE

  DOI：10.1016/j.phytochem.2006.04.001

  日期：2006.6

  chrysosporium ATCC 24725. C. echinulata transformed stemodin (1) to its 7alpha-hydroxy- (2), 7beta-hydroxy- (3) and 3beta-hydroxy- (4) analogues. 2alpha-(N,N-Dimethylcarbamoxy)-13-hydroxystemodane (6) gave 2alpha-(N,N-dimethylcarbamoxy)-6alpha,13-dihydroxystemodane (7) and 2alpha-(N,N-dimethylcarbamoxy)-7alpha,13-dihydroxystemodane (8). Stemodinone (9) yielded 14-hydroxy-(10) and 7beta-hydroxy- (11)

  从植物 Stemodia maritima 中分离出的 Stemodane 和 Stemarane 二萜及其二甲基氨基甲酸酯衍生物被喂养到真菌 Cunninghamella echinulata var. 的生长培养物中。elegans ATCC 8688a 和 Phanerochaete chrysosporium ATCC 24725。C. echinulata 将 Stemodin (1) 转化为它的 7alpha-hydroxy- (2)、7beta-hydroxy- (3) 和 3beta-hydroxy- (4) 类似物。2alpha-(N,N-Dimethylcarbamoxy)-13-hydroxystemodane (6) 得到 2alpha-(N,N-dimethylcarbamoxy)-6alpha,13-dihydroxystemodane (7) 和 2alpha-(N
• Biotransformation of diterpenes and diterpene derivatives by Beauveria bassiana ATCC 7159
  作者：Greg O. Buchanan、Paul B. Reese

  DOI：10.1016/s0031-9422(00)00403-9

  日期：2001.1

  The biohydroxylation of stemodin and stemodinone by Beauveria bassiana ATCC 7159 gave exclusively 2alpha,13,18-trihydroxystemodane and 13,18-dihydroxystemodan-2-one respectively. Stemarin was converted to the novel 1beta,13,19-trihydroxystemarane and 13-hydroxystemarane-19-carboxylic acid. The synthesis and biotransformation of various derivatives of stemodin have also been studied.

  白僵菌 ATCC 7159 对大黄素和大黄酮的生物羟基化分别产生了 2alpha,13,18-trihydroxystemodane 和 13,18-dihydroxystemodan-2-one。Stemarin 被转换为新型 1beta,13,19-trihydroxystemarane 和 13-hydroxystemarane-19-carb 酸。还研究了大黄素的各种衍生物的合成和生物转化。
• Total Synthesis of (±)-Stemodinone via an Efficient Ring-Exchange Strategy
  作者：Tetsuaki Tanaka、Kazuo Murakami、Atsushi Kanda、Debasis Patra、Sachiko Yamamoto、Norifumi Satoh、Sang-Won Kim、S. M. Abdur Rahman、Hiroaki Ohno、Chuzo Iwata

  DOI：10.1021/jo015808w

  日期：2001.10.1

  steps involve an efficient ring-exchange reaction and palladium(0)-catalyzed lactone migration. The ring-exchange strategy for controlling the stereochemistry was based on an initial Diels-Alder reaction to form a new ring followed by cleavage of the original ring. Cleavage of the original ring of the Diels-Alder adduct 9 was achieved by an initial regio- and chemoselective Baeyer-Villiger oxidation followed

  描述了从已知的三环甲基烯烃11的全合成（+/-）-硬脂酮，一种四环戊烷二萜。关键步骤涉及有效的环交换反应和钯（0）催化的内酯迁移。控制立体化学的环交换策略是基于最初的Diels-Alder反应形成一个新环，然后裂解原始环。Diels-Alder加合物9的原始环的裂解是通过最初的区域选择性和化学选择性的Baeyer-Villiger氧化，然后是我们报道的Pd（0）催化的内酯迁移反应实现的。
• Stemodane skeletal rearrangement: chemistry and microbial transformation
  作者：Glenroy D.A. Martin、William F. Reynolds、Paul B. Reese

  DOI：10.1016/j.phytochem.2005.02.019

  日期：2005.4

  Solvolytic rearrangement of the C/D ring system of the tetracyclic diterpenoid stemodinone (2) afforded the compounds 15(13-->12)abeo-13beta-hydroxystemaran-2-one (5) and 15(8-->9)abeo-8beta(H)-12beta-hydroxystachan-2-one (10). Terpene 5 possesses a novel diterpene skeleton. Oxidation of these compounds yielded their respective diketones. Bioconversion of 5 by Rhizopus oryzae yielded 15(13-->12)abeo-7beta

  四环二萜类固醇甾酮 (2) 的 C/D 环系统的溶剂分解重排得到化合物 15(13-->12)abeo-13beta-hydroxystemaran-2-one (5) 和 15(8-->9)abeo -8beta(H)-12beta-hydroxystachan-2-one (10)。萜烯 5 具有新的二萜骨架。这些化合物的氧化产生它们各自的二酮。米根霉对 5 的生物转化产生 15(13-->12)abeo-7beta,13beta-dihydroxystemaran-2-one (18)，而 10 的微生物转化提供 15(8-->9)abeo-8beta(H)- 6alpha,12beta-dihydroxystachan-2-one (19), 15(8-->9)abeo-8beta(H)-7beta,12beta-dihydroxystachan-2-one (20) 和 15(8-->9)abeo
• Total synthesis of (±)-stemodinone
  作者：Tetsuaki Tanaka、Kazuo Murakami、Atsushi Kanda、Debasis Patra、Sachiko Yamamoto、Norifumi Satoh、Sang-Won Kim、Toshimasa Ishida、Yasuko In、Chuzo Iwata

  DOI：10.1016/s0040-4039(97)00173-1

  日期：1997.3

  Starting from methyl-olefin (5), the total synthesis of (±)-stemodinone (2) was achieved through an efficient ring-exchange reaction to control the stereochemistry of C10 followed by A-ring construction and the introduction of three methyl groups.

  从甲基烯烃（5）开始，通过有效的环交换反应控制C10的立体化学，然后进行A环构建和引入三个甲基，实现了（±）-甜菊酮（2）的总合成。