rac-theobroxide

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: rac-theobroxide
• 英文别名: Theobroxide；(1S,2R,5S,6R)-3-methyl-7-oxabicyclo[4.1.0]hept-3-ene-2,5-diol
• 化学式: C₇H₁₀O₃
• 分子量: 142.155
• InChiKey: OICXPDKRWDNGQZ-WNJXEPBRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -1.2
• 重原子数：
  10
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  53
• 氢给体数：
  2
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  rac-theobroxide 在 咪唑 、 Lipase TL 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 168005.5h， 生成 [(1S,2R,5S,6S)-5-[tert-butyl(dimethyl)silyl]oxy-3-methyl-7-oxabicyclo[4.1.0]hept-3-en-2-yl] acetate
  参考文献：
  名称：

  简洁合成植物生长调节剂可可碱。

  摘要：

  由二氢甲苯分四个步骤合成了一种植物生长调节剂可可碱，可在长时间不诱导的条件下生产马铃薯块茎。

  DOI：

  10.1021/jf0500637
• 作为产物：
  描述：

  (3aR,7R,7aS)-7-hydroxy-2,2-dimethyltetrahydrobenzo[d][1,3]dioxol-5(6H)-one 在 tris(dibenzylideneacetone)dipalladium(0) chloroform complex 吡啶 、 咪唑 、 4-二甲氨基吡啶 、 sodium hydroxide 、 sodium tetrahydroborate 、 copper(l) iodide 、 cerium(III) chloride 、 三苯胂 、 氢氟酸 、 碘 、 二乙胺 作用下， 以 四氢呋喃 、 甲醇 、 四氯化碳 、 N,N-二甲基甲酰胺 、 乙腈 为溶剂， 反应 56.0h， 生成 rac-theobroxide
  参考文献：
  名称：

  The First Synthesis of (−)-Asperpentyn and Efficient Syntheses of (+)-Harveynone, (+)-Epiepoformin and (−)-Theobroxide

  摘要：

  A generally applicable strategy for the synthesis of a range of polyoxygenated cyclohexane natural products has been developed. The enantioselective syntheses of (-)-theobroxide, a polyoxygenated cyclohexane natural compound with potent growth inducing properties in potato microtubers has been achieved via a 1,2 O-silyl migration between trans-hydroxyl groups and a remote hydroxyl directed epoxidation of an enone derived from quinic acid. A thus derived alpha -iodoenone was subjected to Stille coupling with tetramethylstannane to afford the first title compound. A similar strategy enabled a route to the complete asymmetric synthesis of the acetylenic phytotoxin (+)-harveynone. By selective reduction of (-)-theobroxide, (+)-epiepoformin was also prepared in enantiopure form and similarly, stereoselective reduction of (+)-harveynone completed the first enantioselective synthesis of (-)-asperpentyn, another natural compound with antimicrobial activity.

  DOI：

  10.1002/1521-3765(20001103)6:21<3991::aid-chem3991>3.3.co;2-m

文献信息

• Enantioselective Synthesis of Natural Polyoxygenated Cyclohexanes and Cyclohexenes from [(p-Tolylsulfinyl)methyl]-p-quinols
  作者：M. Carmen Carreño、Estíbaliz Merino、María Ribagorda、Álvaro Somoza、Antonio Urbano

  DOI：10.1002/chem.200601330

  日期：2007.1.22

  present in a number of enantiomerically pure (SR)- and (SS)-[(p-tolylsulfinyl)methyl]-p-quinols allowed chemo- and stereocontrolled conjugate additions of different organoaluminium reagents to the cyclohexadienone moiety. The same fragment was also shown to act as an efficient chiral masking carbonyl group, after oxidation to sulfone and retroaddition in basic medium, with elimination of methyl p-tolyl

  对存在于许多对映体纯的（SR）-和（SS）-[（（对-甲苯基亚磺酰基）甲基]-对-喹诺醇中的β-羟基亚砜片段的利用允许将不同的有机铝试剂化学和立体控制的共轭加成到环己二烯酮部分上。在氧化为砜并在碱性介质中逆向加成并消除了甲基对甲苯基砜之后，该片段还显示出可作为有效的手性掩蔽羰基的基团。通过将这两种转化用作关键步骤，可对不同天然产物进行对映体控制的合成，例如二氢表二甲双胍，（-）-葡糖胺O，（+）-表二甲双胍，（-）-可可生物碱和（+）-4-的两种对映体现已实现了表没食子碱A（一种天然产物菜黄素A的差向异构体）。β-羟基砜部分的存在使环状结构变得刚性，在到达天然结构的过程中，可以进行许多立体选择性转化，例如羰基还原，烯酮环氧化或顺式二羟基化。观察到的选择性取决于每个底物中的特定取代基，提供了远端基团对反应物优选的反应构象的优选方法的强烈影响的证据。还合成了天然（+）-harveynone的高
• New Potato Micro-Tuber-Inducing Cyclohexene Compounds Related to Theobroxide from<i>Lasiodiplodia theobromae</i>
  作者：Ryo TAKEI、Kosaku TAKAHASHI、Hideyuki MATSUURA、Kensuke NABETA

  DOI：10.1271/bbb.80171

  日期：2008.8.23

  Two new cyclohexene compounds related to theobroxide (3) were isolated from the mycelia of Lasiodiplodia theobromae OCS71. The structures of these compounds were determined to be (4S,5S)-4,5-dihydroxy-2-methyl-cyclohex-2-enone (1) and (3aS,4R,5S,7aR)-4,5-dihydroxy-7-methyl-3a,4,5,7a-tetrahydrobenzo[1,3]dioxol-2-one (2) by means of spectroscopic analyses and chemical correlation to 3. Compound 2 was shown to take up the carbonate ion to form a carbonic acid ester non-enzymatically. The compounds also showed potato micro-tuber-inducing activities at a concentration of 10−3  m, using a culture of single-node segments of potato stems in vitro.

  从 Lasiodiplodia theobromae OCS71 的菌丝体中分离出两种与可可碱（3）有关的新环己烯化合物。通过光谱分析和与 3 的化学相关性，确定这些化合物的结构为 (4S,5S)-4,5-二羟基-2-甲基-环己-2-烯酮 (1) 和 (3aS,4R,5S,7aR)-4,5-二羟基-7-甲基-3a,4,5,7a-四氢苯并[1,3]二恶茂-2-酮 (2)。结果表明，化合物 2 可以非酶促方式吸收碳酸根离子，形成碳酸酯。利用马铃薯茎单节段的离体培养，在 10-3 m 的浓度下，化合物还显示出马铃薯微瘤胃诱导活性。
• The enantiodivergent total synthesis of natural and unnatural enantiomers of theobroxide
  作者：Takashi Kamikubo、Kunio Ogasawara

  DOI：10.1016/0040-4039(95)00131-u

  日期：1995.3

  Both enantiomers of theobroxide, a potato micro-tuber inducing substance isolated from Lasiodiplodia theobromae, have been synthesized from a common chiral building block serving as a chiral equivalent of 1,4-dihydroxy-2,5-cyclohexadiene. The synthesis has verified the proposed structure and the absolute configuration.

  从一种常见的手性结构单元，即1,4-二羟基-2,5-环己二烯的手性等效物，合成了theobroxide的两种对映异构体，这是一种从马铃薯红孢杆菌中分离出来的马铃薯微块茎诱导物质。综合已经验证了所提出的结构和绝对构型。
• Isolation and Structural Elucidation of a New Cyclohexenone Compound from<i>Lasiodiplodia theobromae</i>
  作者：Naoki KITAOKA、Kensuke NABETA、Hideyuki MATSUURA

  DOI：10.1271/bbb.90218

  日期：2009.8.23

  A new cyclohexenone compound was isolated as a mixture of enantiomers from a culture filtrate of Lasiodiplodia theobromae. The relative structure was determined to be 4,5-dihydroxy-3-methyl-cyclohex-2-enone on the basis of MS, 1H-NMR, and 13C-NMR spectroscopic analyses, including 2D-NMR experiments. Resolution of the enantiomers was conducted by a coupling reaction with (S)-MTPA-Cl followed by HPLC separation.

  从 Lasiodiplodia theobromae 的培养滤液中分离出一种新的环己烯酮化合物，它是一种对映体混合物。根据 MS、1H-NMR 和 13C-NMR 光谱分析，包括 2D-NMR 实验，确定其相对结构为 4,5-二羟基-3-甲基-环己-2-烯酮。通过与 (S)-MTPA-Cl 发生偶联反应，然后进行高效液相色谱分离，对对映体进行了解析。
• (+)-epi-Epoformin, a Phytotoxic Fungal Cyclohexenepoxide: Structure Activity Relationships
  作者：Antonio Cala、Marco Masi、Alessio Cimmino、José Molinillo、Francisco Macias、Antonio Evidente

  DOI：10.3390/molecules23071529

  日期：——

  (+)-epi-Epoformin (1), is a fungal cyclohexene epoxide isolated together with diplopimarane and sphaeropsidins A and C, a nor-ent-pimarane and two pimaranes, from the culture filtrates of Diplodia quercivora, a fungal pathogen for cork oak in Sardinia, Italy. Compound 1 possesses a plethora of biological activities, including antifungal, zootoxic and phytotoxic activity. The last activity and the peculiar structural feature of 1 suggested to carry out a structure activity relationship study, preparing eight key hemisynthetic derivatives and the phytotoxicity was assayed. The complete spectroscopic characterization and the activity in the etiolated wheat coleoptile bioassay of all the compounds is reported. Most of the compounds inhibited growth and some of them had comparable or higher activity than the natural product and the reference herbicide Logran. As regards the structure-activity relationship, the carbonyl proved to be essential for their activity of 1, as well as the conjugated double bond, while the epoxide could be altered with no significant loss.

  (+)-表-表埃波霉素（1）是一种真菌环己烯环氧化物，与双孢松烷和球形孢子素A和C、一种去甲表松烷和两种松烷一起从意大利撒丁岛软木栎的一种真菌病原体双孢松的菌落滤液中分离出来。化合物1具有多种生物活性，包括抗真菌、动物毒性和植物毒性活性。最后一种活性以及1的独特结构特征表明需要进行结构活性关系研究，制备了8种关键半合成衍生物，并检测了植物毒性。报告了所有化合物的完整光谱表征和在萎黄病小麦胚芽鞘生物测定中的活性。大多数化合物抑制了生长，其中一些化合物的活性与天然产物和参考除草剂Logran相当或更高。关于结构活性关系，羰基和共轭双键被证明对1的活性至关重要，而环氧化物可以改变而不会显着损失。