(3R,7R,11R,15R)-1,11,16-trihydroxy-3,7,11,15-tetramethylhexadecan-4-one | 868836-97-9

• 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: (3R,7R,11R,15R)-1,11,16-trihydroxy-3,7,11,15-tetramethylhexadecan-4-one
• 英文别名: Phytophthora mating (3R,7R,11R,15R)-hormone α1
• CAS: 868836-97-9
• 化学式: C₂₀H₄₀O₄
• 分子量: 344.535
• InChiKey: KVWYIWRSDKQRFM-SOAMZJECSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  24
• 可旋转键数：
  15
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.95
• 拓扑面积：
  77.8
• 氢给体数：
  3
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (3R,7R,11R,15R)-1,11,16-trihydroxy-3,7,11,15-tetramethylhexadecan-4-one 在 sodium tetrahydroborate 作用下， 以 甲醇 为溶剂， 反应 14.0h， 以0.05 mg的产率得到
  参考文献：
  名称：

  Structure–activity relationship of α hormones, the mating factors of phytopathogen Phytophthora

  摘要：

  The mating hormones alpha 1 and alpha 2 induce sexual reproduction of the phytopathogenic genus Phytophthora. To demonstrate the structural elements responsible to hormonal activity, 17 derivatives of alpha 1 and alpha 2 were synthesized and their hormonal activity (oospore-inducing activity) was evaluated. The terminal ester derivatives of alpha 1 (diacetate and dibenzoate) retained the hormonal activity, whereas a dicarbamate derivative completely suppressed the activity. Even monocarbamates showed weak activities; among them the 1-O-carbamate was less active than 16-O-carbamate, suggesting that the 1-OH group is a little more important than 16-OH. Dihydro, dehydro, and demethyl derivatives exhibited the minimum level of activity. Surviving activity of 15-epi-alpha 1 suggested a less importance of this stereochemistry. Contrary to alpha 1, not only the terminal diacetate derivative but also monoacetates of alpha 2 exhibited no or little activity. Among the monoacetates, 1-O-acetyl-alpha 2 exhibited little yet relatively better activity than the others. No activity was observed for mono- and dicarbamoyl derivatives of alpha 2. Dihydro alpha 2 with the saturated double bond lost most of the activity. These findings suggest that both the mating hormones alpha 1 and alpha 2 require most of the functional (hydroxyl, keto, and olefinic) groups they possess in their natural form for inducing the sexual reproduction of Phytophthora. (C) 2011 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.bmc.2011.12.015
• 作为产物：
  描述：

  (-)-香茅醛 在 吡啶 、 2,6-二甲基吡啶 、 4-二甲氨基吡啶 、 platinum(IV) oxide 、 四甲基乙二胺 、 RuCl₂[(S)-(DM-BINAP)][(S)-DAIPEN] 、 四丁基氟化铵 、 氢气 、 双氧水 、 仲丁基锂 、 碳酸氢钠 、 potassium carbonate 、 戴斯-马丁氧化剂 、 臭氧 、 溶剂黄146 、 lithium tri-t-butoxyaluminum hydride 、 三乙胺 、 N,N-二异丙基乙胺 、 lithium chloride 、 sodium hydroxide 、 鹰爪豆碱 作用下， 以 四氢呋喃 、 乙醚 、 正己烷 、 二氯甲烷 、 甲基叔丁基醚 、 环己烷 、 水 、 乙酸乙酯 、 异丙醇 、 甲苯 为溶剂， -78.0~150.0 ℃ 、1.0 MPa 条件下， 反应 123.11h， 生成 (3R,7R,11R,15R)-1,11,16-trihydroxy-3,7,11,15-tetramethylhexadecan-4-one
  参考文献：
  名称：

  利用锂化/硼烷基化反应短立体选择性合成疫霉通用交配激素α1

  摘要：

  毒性植物病原菌疫霉的通用交配激素α1已通过12个步骤合成，总产率为28％。密钥C  C键形成步骤涉及使用两个锂化/硼基化反应来耦合在一起对映体富集积木，其中之一也设置在C11叔醇的立体化学。详细分析表明，目标分子的非对映异构体纯度> 91％，是迄今为止获得的最高纯度。

  DOI：

  10.1002/anie.201400714

文献信息

• Total Synthesis of <i>Phytophthora</i> Mating Hormone α1
  作者：Shun-Yi Wang、Ping Song、Li-Yan Chan、Teck-Peng Loh

  DOI：10.1021/ol102177j

  日期：2010.11.19

  Total synthesis of Phytophthora mating hormone α1 (1) has been demonstrated. The required stereochemistries (methyl) are achieved by applying CuI-(S)-Tol-BINAP-catalyzed conjugate addition of Grignard reagents to α,β-unsaturated esters.

  已经证明了疫霉交配激素α1（1）的全合成。所需的立体化学（甲基）是通过将Cuignard试剂的CuI-（S）-Tol-BINAP催化的共轭加成物加到α，β-不饱和酯上而实现的。
• Synthesis and Spectroscopic Analysis of a Stereoisomer Library of the Phytophthora Mating Hormone α1 and Derived Bis-Mosher Esters
  作者：Reena Bajpai、Dennis P. Curran

  DOI：10.1021/ja2082679

  日期：2011.12.21

  Fluorous mixture synthesis provided all eight diastereomers of the phytophthora hormone alpha 1 with the R configuration at C11 as individual samples after demixing and detagging. The library of all possible bis-Mosher esters (16) was then made by esterification. Complete sets of H-1, C-13, and (for the Mosher esters) F-19 NMR spectra were recorded, assigned, and compared with each other and with published spectra. Not all of the spectra are unique, and the H-1 NMR spectra of the Mosher esters provided the most information. The previous assignment of the natural sample as an "all-R" stereoisomer mixed with its 3S-epimer was confirmed.
• Structure–activity relationship of α hormones, the mating factors of phytopathogen Phytophthora
  作者：Shylaja D. Molli、Jianhua Qi、Arata Yajima、Keisuke Shikai、Tadashi Imaoka、Tomoo Nukada、Goro Yabuta、Makoto Ojika

  DOI：10.1016/j.bmc.2011.12.015

  日期：2012.1

  The mating hormones alpha 1 and alpha 2 induce sexual reproduction of the phytopathogenic genus Phytophthora. To demonstrate the structural elements responsible to hormonal activity, 17 derivatives of alpha 1 and alpha 2 were synthesized and their hormonal activity (oospore-inducing activity) was evaluated. The terminal ester derivatives of alpha 1 (diacetate and dibenzoate) retained the hormonal activity, whereas a dicarbamate derivative completely suppressed the activity. Even monocarbamates showed weak activities; among them the 1-O-carbamate was less active than 16-O-carbamate, suggesting that the 1-OH group is a little more important than 16-OH. Dihydro, dehydro, and demethyl derivatives exhibited the minimum level of activity. Surviving activity of 15-epi-alpha 1 suggested a less importance of this stereochemistry. Contrary to alpha 1, not only the terminal diacetate derivative but also monoacetates of alpha 2 exhibited no or little activity. Among the monoacetates, 1-O-acetyl-alpha 2 exhibited little yet relatively better activity than the others. No activity was observed for mono- and dicarbamoyl derivatives of alpha 2. Dihydro alpha 2 with the saturated double bond lost most of the activity. These findings suggest that both the mating hormones alpha 1 and alpha 2 require most of the functional (hydroxyl, keto, and olefinic) groups they possess in their natural form for inducing the sexual reproduction of Phytophthora. (C) 2011 Elsevier Ltd. All rights reserved.
• Short Stereoselective Synthesis of the<i>Phytophthora</i>Universal Mating Hormone α1 Using Lithiation/Borylation Reactions
  作者：Alexander P. Pulis、Philipp Fackler、Varinder K. Aggarwal

  DOI：10.1002/anie.201400714

  日期：2014.4.22

  The universal mating hormone α 1 of the virulent plant pathogen Phytophthora has been synthesized in 12 steps and 28 % overall yield. Key CC bond‐forming steps involved the use of two lithiation/borylation reactions to couple together enantioenriched building blocks, one of which also set up the stereochemistry of the tertiary alcohol at C11. Detailed analysis showed that the diastereomeric purity

  毒性植物病原菌疫霉的通用交配激素α1已通过12个步骤合成，总产率为28％。密钥C  C键形成步骤涉及使用两个锂化/硼基化反应来耦合在一起对映体富集积木，其中之一也设置在C11叔醇的立体化学。详细分析表明，目标分子的非对映异构体纯度> 91％，是迄今为止获得的最高纯度。