(2S,3S)-1-<(tert-butyldiphenylsilyl)oxy>-2-methylhex-5-en-3-ol | 106296-60-0

• 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: (2S,3S)-1-<(tert-butyldiphenylsilyl)oxy>-2-methylhex-5-en-3-ol
• 英文别名: (2S,3S)-1-(tert-butyldiphenylsilyloxy)-2-methylhex-5-en-3-ol；(2S,3S)-1-(t-butyldiphenylsilyloxy)-2-methylhex-5-en-3-ol；(2S,3S)-1-[(tert-butyldiphenylsilyl)oxy]-2-methylhex-5-en-3-ol；(2S,3S)-1-[tert-butyl(diphenyl)silyl]oxy-2-methylhex-5-en-3-ol
• CAS: 106296-60-0
• 化学式: C₂₃H₃₂O₂Si
• 分子量: 368.591
• InChiKey: JKUPTISZYOJMLN-UGKGYDQZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.14
• 重原子数：
  26
• 可旋转键数：
  9
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.39
• 拓扑面积：
  29.5
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (2S,3S)-1-<(tert-butyldiphenylsilyl)oxy>-2-methylhex-5-en-3-ol 在 吡啶 、 2,6-二甲基吡啶 、 4-二甲氨基吡啶 、 Cl₂Ru(C₃H₅N₂(Mes)2)(C₁₀H₁₂O) 、 三氟化硼乙醚 、 臭氧 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 16.0h， 生成 ethyl (2E,6E,11S,12S)-5,9-diacetyloxy-11-[tert-butyl(dimethyl)silyl]oxy-13-[tert-butyl(diphenyl)silyl]oxy-12-methyltrideca-2,6-dienoate
  参考文献：
  名称：

  四纤蛋白：C1-C13，C15-C25和C27-C40片段的合成。

  摘要：

  [结构：见正文]醛的化学选择性交叉复分解反应和对映选择性烯丙基钛化反应已用于制备四纤蛋白的C1-C13，C15-C26和C27-C40片段。

  DOI：

  10.1021/ol048862i
• 作为产物：
  描述：

  (2S)-3-{[tert-butyl(diphenyl)silyl]oxy}-2-methylpropanal 、 alkaline earth salt of/the/ methylsulfuric acid 以 乙醚 为溶剂， 以87%的产率得到(2S,3S)-1-<(tert-butyldiphenylsilyl)oxy>-2-methylhex-5-en-3-ol
  参考文献：
  名称：

  四纤蛋白：C1-C13，C15-C25和C27-C40片段的合成。

  摘要：

  [结构：见正文]醛的化学选择性交叉复分解反应和对映选择性烯丙基钛化反应已用于制备四纤蛋白的C1-C13，C15-C26和C27-C40片段。

  DOI：

  10.1021/ol048862i

文献信息

• Synthesis and biological activities of the tris-oxazole macrolactone analogs of mycalolides
  作者：Masaki Kita、Hirotaka Oka、Akihiro Usui、Tomoya Ishitsuka、Yuzo Mogi、Hidekazu Watanabe、Hideo Kigoshi

  DOI：10.1016/j.tet.2012.08.012

  日期：2012.10

  Mycalolides are tris-oxazole macrolides isolated from the marine sponge Mycale sp., which shows cytotoxic, antifungal, and actin-depolymerizing activities. To develop an efficient synthetic route of mycalolides and to evaluate its functional mechanism of biological activities, tris-oxazole macrolactone analogs of mycalolides were synthesized through the use of ring-closing metathesis (RCM). The presence/absence

  Mycalolides是从海洋海绵Mycale sp。分离得到的三恶唑大环内酯类，具有细胞毒性，抗真菌和肌动蛋白解聚活性。为了开发一种高效的Mycalolides合成路线并评估其生物学活性的功能机制，通过使用闭环复分解（RCM）合成了Mycalolides的tris-恶唑大内酯类似物。C3上是否存在保护基，溶剂极性和反应温度均显着影响RCM的立体选择性（E / Z = 2.5 / 1.0–1.0 / 2.5）。19 E和19 Z-立体异构体均显示出对肿瘤细胞的中等细胞毒性，但均未显示出显着的肌动蛋白解聚特性或对病原真菌的抗真菌活性。因此，建议侧链（肌动蛋白结合）部分和大内酯部分对于母体分子的有效生物活性都是必不可少的。
• Iridium-Catalyzed Allylation of Chiral β-Stereogenic Alcohols: Bypassing Discrete Formation of Epimerizable Aldehydes
  作者：Daniel C. Schmitt、Anne-Marie R. Dechert-Schmitt、Michael J. Krische

  DOI：10.1021/ol3030692

  日期：2012.12.21

  4-dinitro-C,O-benzoate complex modified by (R)- or (S)-Cl,MeO-BIPHEP promotes the transfer hydrogenative coupling of allyl acetate to β-stereogenic alcohols with good to excellent levels of catalyst-directed diastereoselectivity to furnish homoallylic alcohols. Remote electronic effects of the C,O-benzoate of the catalyst play a critical role in suppressing epimerization of the transient α-stereogenic

  ( R )-或( S )-Cl,MeO-BIPHEP修饰的环金属化π-烯丙基3,4-二硝基-C,O-苯甲酸配合物促进乙酸烯丙酯向β-立体醇的转移加氢偶联，具有良好到优异的性能提供高烯丙醇的催化剂导向的非对映选择性水平。催化剂的C,O-苯甲酸酯的远程电子效应在抑制瞬态 α-立体醛的差向异构化方面起着关键作用。
• SYNTHESIS OF (+)-B-ALLYLDIISOPINOCAMPHEYLBORANE AND ITS REACTION WITH ALDEHYDES
  作者：Sun, Huikai、Roush, William R.

  DOI：10.15227/orgsyn.088.0087

  日期：——
• Asymmetric synthesis using tartrate ester modified allylboronates. 2. Single and double asymmetric reactions with alkoxy-substituted aldehydes
  作者：William R. Roush、Lee K. Hoong、Michelle A. J. Palmer、Julie A. Straub、Alan D. Palkowitz

  DOI：10.1021/jo00300a032

  日期：1990.6
• N,N'-Bis(2,2,2-trifluoroethyl)-N,N'-ethylenetartramide: An Improved Chiral Auxiliary for the Asymmetric Allylboration Reaction
  作者：William R. Roush、Paul T. Grover

  DOI：10.1021/jo00117a036

  日期：1995.6

  N,N-Bis(2,2,2-trifluoroethyl)-N,N'-ethylenetartramide (8), synthesized by a simple four-step sequence from ethylenediamine and benzylidenetartaric acid, was designed in anticipation that the derived allylboronates 9-11 would display enhanced reactivity owing to the inductive effect of the N-trifluoroethyl substituents that would increase the Lewis acidity of the boron atom of the B-allyl-1,3,2-dioxaborolanes. Reagents 9-11 were synthesized by transesterification of 8 with the crystalline and easily purified allylboronate diethanolamine complexes 13, 19, and 25. Allylboronate 9 is ca. 100-fold more reactive than 6 and is also substantially more useful than the previously reported allyboronate 4, which suffers from very poor solubility in toluene at -78 degrees C. Most importantly, allylboronates 9-11 are significantly more enantioselective than the parent tartrate allylboronates 1-3 and rank among the most highly enantioselective allylboron reagents yet reported. Reactions of 9-11 with aldehydes are performed in THF at- -78 or -55 degrees C for 5-12 h periods. The enantioselectivity realized in reactions with achiral aldehydes is 92-95% ee (Table 2), and excellent diastereoselectivity is achieved in double asymmetric reactions with chiral aldehydes 15a, 15b, and 33 (Tables 3 and 4). For example, 16 and 28 are now available with a minimum selectivity of 92% from reactions of 15a and 15b with allylboronate 9, while the crotylboration products 29, 30, and 31 are available with a minimum selectivity of 90% (usually greater than or equal to 95%) from reactions of 15a and 15b with crotylboronates 10 and 11; the fourth isomer, 32a, is available with 83% selectivity. Chiral reagents 9-11 thus appear well suited for application to complex problems in organic synthesis.