(R)-5-(tert-butyldimethylsilyl)oxy-4-methylpentanal | 105859-49-2

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: (R)-5-(tert-butyldimethylsilyl)oxy-4-methylpentanal
• 英文别名: (S)-5-((tert-butyldimethylsilyl)oxy)-4-methylpentanal；(S)-5-(t-butyldimethylsilyloxy)-4-methylpentanal；(4S)-5-[tert-butyl(dimethyl)silyl]oxy-4-methylpentanal
• CAS: 105859-49-2
• 化学式: C₁₂H₂₆O₂Si
• 分子量: 230.423
• InChiKey: RMBQJVZBVJJOGJ-NSHDSACASA-N

物化性质

• 沸点：
  255.7±23.0 °C(Predicted)
• 密度：
  0.864±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.62
• 重原子数：
  15
• 可旋转键数：
  7
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.92
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (R)-5-(tert-butyldimethylsilyl)oxy-4-methylpentanal 在 正丁基锂 、 草酰氯 、 四丁基氟化铵 、 二甲基亚砜 、 三乙胺 、 红铝 作用下， 以 四氢呋喃 、 乙醚 为溶剂， 生成
  参考文献：
  名称：

  Acyclic stereocontrol in catalyzed intramolecular Diels-Alder cyclizations leading to octahydronaphthalenecarboxaldehydes

  摘要：

  DOI：

  10.1021/ja00238a030
• 作为产物：
  描述：

  methyl (4S)-5-[tert-butyl(dimethyl)silyl]oxy-4-methylpentanoate 在 二异丁基氢化铝 作用下， 以 甲苯 为溶剂， 反应 2.0h， 以100%的产率得到(R)-5-(tert-butyldimethylsilyl)oxy-4-methylpentanal
  参考文献：
  名称：

  首次合成（S）-（+）-月桂酸，一种从膜虫科（Hymenochaetaceae sp。）分离的DNA聚合酶λ抑制剂。

  摘要：

  从真菌Hymenochaetaceae sp。的培养物中分离得到的处女膜酸是DNA聚合酶λ的特异性抑制剂。（S）-（+）-庚二酸的首次合成是由反式1,4-环己烷二甲醇和（R）-（-）-3-羟基异丁酸甲酯开始进行的，并以Julia-Kocienski烯化为关键步。

  DOI：

  10.1080/09168451.2017.1406302

文献信息

• Total Synthesis of (+)-18-<i>epi</i>-Latrunculol A: Development of a Synthetic Route
  作者：Brett D. Williams、Amos B. Smith

  DOI：10.1021/jo501733m

  日期：2014.10.3

  The evolution of an enantioselective total synthesis of (+)-18-epi-latrunculol A, a congener of the marine-sponge-derived latrunculins A and B, is reported. Key steps include a late-stage Mitsunobu macrolactonization to construct the 16-membered macrolactone, a mild Carreira alkynylation to unite the northern and southern hemispheres, a diastereoselective, acid-mediated δ-hydroxy enone cyclization/equilibration

  报告了 (+)-18- epi -latrunculol A（海洋海绵衍生的 latrunculins A 和 B 的同系物）的对映选择性全合成的演变。关键步骤包括后期 Mitsunobu 大环内酯化以构建 16 元大环内酯、温和的 Carreira 炔基化以统一北半球和南半球、非对映选择性、酸介导的 δ-羟基烯酮环化/平衡序列，以及功能组-耐受交叉复分解以获得烯酮环化前体。
• Synthesis of a C1−C21 Subunit of the Protein Phosphatase Inhibitor Tautomycin:  A Formal Total Synthesis
  作者：James A. Marshall、Mathew M. Yanik

  DOI：10.1021/jo0056951

  日期：2001.2.1

  The synthesis of a C1-C21 subunit of tautomycin is described. The convergent route employs enantioenriched allenylstannane and zinc reagents derived from (S)-3-butyn-2-ol methanesulfonate. These reagents react with appropriate aldehyde segments to yield syn and anti adducts with high diastereoselectivity. The derived lithioalkynes are joined stepwise to a CO equivalent, (MeONMe)2C=O, to afford an intermediate

  描述了互变霉素C1-C21亚基的合成。收敛路线采用了对映体富集的烯丙基锡烷和衍生自（S）-3-butyn-2-ol甲磺酸盐的锌试剂。这些试剂与适当的醛链段反应，以高非对映选择性产生顺式和反加合物。将衍生的硫代炔烃逐步连接至CO当量（MeONMe）2 C ＝ O，以提供中间体酮，该中间体酮在酸处理后转化为互变异构体的核心螺缩酮部分。通过将上述烯丙基锌试剂另一种添加到螺酮醛中来进行链延长，以高非对映选择性进行，以安装剩余的立体中心。所得的炔丙醇加合物通过炔烃的分子内氢化硅烷化和衍生的五元硅氧烷的Tamoo氧化而转化为甲基酮。该酮被证明与张伯林在先前的互变异构全合成中使用的中间体相同。
• 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.
• Total Synthesis of (+)-18-<i>epi-</i>Latrunculol A
  作者：Brett D. Williams、Amos B. Smith

  DOI：10.1021/ol4021892

  日期：2013.9.6

  An enantioselective total synthesis of the cytotoxic latrunculin congener (+)-18-epi-latrunculol A has been achieved. Key steps in the synthetic route include an acid-mediated enone cyclization/equilibration sequence, a Carreira alkynylation, and a late-stage Mitsunobu macrolactonization to construct the macrolide skeleton.
• Nicolaou; Sarabia; Ninkovic, Angewandte Chemie - International Edition in English, 1998, vol. 37, # 1-2, p. 81 - 84
  作者：Nicolaou、Sarabia、Ninkovic、Finlay、Boddy

  DOI：——

  日期：——