(2R,4R)-2-Methyl-4-triethylsilanyloxy-pentanal | 681830-17-1

• 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: (2R,4R)-2-Methyl-4-triethylsilanyloxy-pentanal
• 英文别名: (2R,4R)-2-methyl-4-triethylsilyloxypentanal
• CAS: 681830-17-1
• 化学式: C₁₂H₂₆O₂Si
• 分子量: 230.423
• InChiKey: HCRKWVRCRJKHCA-VXGBXAGGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.62
• 重原子数：
  15
• 可旋转键数：
  8
• 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：

  (2R,4R)-2-Methyl-4-triethylsilanyloxy-pentanal 在 2,6-二甲基吡啶 、 三氟甲磺酸二丁硼 、 三乙胺 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 反应 2.17h， 生成 (R)-4-Benzyl-3-[(2R,3S,4R,6R)-2-(4-methoxy-benzyloxy)-4-methyl-3,6-bis-triethylsilanyloxy-heptanoyl]-oxazolidin-2-one
  参考文献：
  名称：

  对两性霉素B1的合成研究：C9-C26片段的合成。

  摘要：

  [反应：见正文]描述了两性霉素B1的C9-C26部分的合成。弗莱明烯丙基化随后消除被用于构建C 13 -C 15二烯部分。在C13-C15二烯官能团存在的情况下，利用Sharpless不对称二羟基化技术对苯乙烯衍生的烯烃进行区域选择性官能化。开发了高度非对映选择性的醛醇缩合反应以建立C18立体化学。

  DOI：

  10.1021/ol051544e
• 作为产物：
  描述：

  三乙基氯硅烷 在 四丙基高钌酸铵 4-二甲氨基吡啶 、 正丁基锂 、 ammonia borane 、 N-甲基吲哚酮 、 三乙胺 、 二异丙胺 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 为溶剂， 反应 14.5h， 生成 (2R,4R)-2-Methyl-4-triethylsilanyloxy-pentanal
  参考文献：
  名称：

  Unified Synthesis of C₁₉−C₂₆ Subunits of Amphidinolides B₁, B₂, and B₃ by Exploiting Unexpected Stereochemical Differences in Crimmins' and Evans' Aldol Reactions

  摘要：

  The efficient synthesis of the C-19-C-26 subunit of amphidinolide B-1 and B-2 has been completed using a boron-mediated aldol reaction. The synthesis of the C-19-C-26 subunit of amphidinolide B-3 has also been accomplished through an unexpected anti aldol reaction using a titanium-mediated process. In addition, the first reported examples of a stereochemical discrepancy between the Evans' boron-mediated oxazolidinone and the Crimmins' titanium-mediated oxazolidinethione aldol reactions are disclosed. A working hypothesis is put forth to explain the results.

  DOI：

  10.1021/jo035829l

文献信息

• Total Syntheses of Amphidinolides B1, B4, G1, H1 and Structure Revision of Amphidinolide H2
  作者：Alois Fürstner、Laure C. Bouchez、Louis Morency、Jaques-Alexis Funel、Vilnis Liepins、François-Hugues Porée、Ryan Gilmour、Daniel Laurich、Florent Beaufils、Minoru Tamiya

  DOI：10.1002/chem.200802067

  日期：2009.4.14

  unselective “chemist” when it comes to making the highly cytotoxic amphidinolide macrolides of the B/G/H series. To date, 16 different such compounds have been isolated, all of which could now be approached by a highly convergent and largely catalysis‐based route (see figure). This notion is exemplified by the total synthesis of five prototype members of this family.

  在生产具有高细胞毒性的B / G / H系列安非他命类大环内酯类药物时，自然界是一个非选择性的“化学家”。迄今为止，已分离出16种不同的此类化合物，现在可以通过高度聚合且主要基于催化作用的途径来接近所有这些化合物（见图）。该族的五个原型成员的总合成就是这一概念的例证。
• Amphidinolide B: Total Synthesis, Structural Investigation, and Biological Evaluation
  作者：Liang Lu、Wei Zhang、Sangkil Nam、David A. Horne、Richard Jove、Rich G. Carter

  DOI：10.1021/jo3026077

  日期：2013.3.15

  The total syntheses of amphidinolide B-1 and the proposed structure of amphidinolide B-2 have been accomplished. Key aspects of this work include the development of a practical, non-transitionmetal-mediated method for the construction of the C-13-C-15 diene, the identification of alpha-chelation and dipole minimization models for diastereoselective methyl ketone aldol reactions, the discovery of a spontaneous Horner-Wadsworth-Emmons macrocyclization strategy, and the development of a novel late stage method for construction of an allylic epoxide moiety. The originally proposed structure for amphidinolide B-2 and diastereomers thereof display potent antitumor activities with IC50 values ranging from 3.3 to 94.5 nM against human solid and blood tumor cells. Of the different stereoisomers, the proposed structure of amphidinolide B-2 is over 12-fold more potent than the C-8,C-9-epimer and C-18-epimer in human DU145 prostate cancer cells. These data suggest that the epoxide stereochemistry is a significant factor for anticancer activity.
• Total Synthesis of Cytotoxic Macrolide Amphidinolide B₁ and the Proposed Structure of Amphidinolide B₂
  作者：Liang Lu、Wei Zhang、Rich G. Carter

  DOI：10.1021/ja803012n

  日期：2008.6.1

  The first enantioselective total syntheses of cytotoxic macrolide amphidinolide B, and the proposed structure for amphidinolide B-2 have been accomplished. Key features of the syntheses include a diastereoselective aldol condensation, a spontaneous Wadsworth-Emmons `macrocyclization and a directed epoxidation/elimination sequence.
• Synthetic Studies toward Amphidinolide B₁:  Synthesis of the C₉−C₂₆ Fragment
  作者：Wei Zhang、Rich G. Carter

  DOI：10.1021/ol051544e

  日期：2005.9.1

  [reaction: see text] The synthesis of the C9-C26 portion of amphidinolide B1 is described. A Fleming allylation followed by elimination was employed for the construction of the C13-C15 diene portion. Sharpless asymmetric dihydroxylation was utilized for regioselective functionalization of a styrene-derived alkene, in the presence of the C13-C15 diene functionality. A highly diastereoselective aldol

  [反应：见正文]描述了两性霉素B1的C9-C26部分的合成。弗莱明烯丙基化随后消除被用于构建C 13 -C 15二烯部分。在C13-C15二烯官能团存在的情况下，利用Sharpless不对称二羟基化技术对苯乙烯衍生的烯烃进行区域选择性官能化。开发了高度非对映选择性的醛醇缩合反应以建立C18立体化学。
• Unified Synthesis of C₁₉−C₂₆ Subunits of Amphidinolides B₁, B₂, and B₃ by Exploiting Unexpected Stereochemical Differences in Crimmins' and Evans' Aldol Reactions
  作者：Wei Zhang、Rich G. Carter、Alexandre F. T. Yokochi

  DOI：10.1021/jo035829l

  日期：2004.4.1

  The efficient synthesis of the C-19-C-26 subunit of amphidinolide B-1 and B-2 has been completed using a boron-mediated aldol reaction. The synthesis of the C-19-C-26 subunit of amphidinolide B-3 has also been accomplished through an unexpected anti aldol reaction using a titanium-mediated process. In addition, the first reported examples of a stereochemical discrepancy between the Evans' boron-mediated oxazolidinone and the Crimmins' titanium-mediated oxazolidinethione aldol reactions are disclosed. A working hypothesis is put forth to explain the results.