(4R) 5-(t-butyldiphenylsilyloxy)-4-methylpentan-1-ol | 164907-39-5

• 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: (4R) 5-(t-butyldiphenylsilyloxy)-4-methylpentan-1-ol
• 英文别名: (R)-5-(tert-butyldiphenylsilyloxy)-4-methyl-pentanol；(R)-5-(tert-butyldiphenylsilyloxy)-4-methylpentan-1-ol；(4R)-5-(tert-butyldiphenylsilyloxy)-4-methyl-1-pentanol；(4R)-5-[1-(tert-butyl)-1,1-diphenylsilyl]oxy-4-methylpentan-1-ol；(4R)-5-{[tert-Butyl(diphenyl)silyl]oxy}-4-methylpentan-1-ol；(4R)-5-[tert-butyl(diphenyl)silyl]oxy-4-methylpentan-1-ol
• CAS: 164907-39-5
• 化学式: C₂₂H₃₂O₂Si
• 分子量: 356.58
• InChiKey: LTBRSVIOCXYIRK-LJQANCHMSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.97
• 重原子数：
  25
• 可旋转键数：
  9
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.45
• 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：

  (4R) 5-(t-butyldiphenylsilyloxy)-4-methylpentan-1-ol 在 palladium on activated charcoal 2,6-二甲基吡啶 、 lithium hydroxide 、 N-羟基-7-氮杂苯并三氮唑 、 草酰氯 、 三氟化硼乙醚 、 四丁基氟化铵 、 氢气 、 三乙基硅基三氟甲磺酸酯 、 1,8-双二甲氨基萘 、 二甲基亚砜 、 盐酸-N-乙基-Nˊ-(3-二甲氨基丙基)碳二亚胺 、 三乙胺 、 N,N-二异丙基乙胺 、 三氟乙酸 作用下， 以 四氢呋喃 、 甲醇 、 乙醚 、 乙醇 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， -100.0~25.0 ℃ 、101.33 kPa 条件下， 反应 105.08h， 生成 (S)-2-((3S,4R,7S)-3-Hydroxy-7-methoxy-2,2,4-trimethyl-decanoylamino)-propionic acid methyl ester
  参考文献：
  名称：

  卤肽素的全合成：卤肽素D的分离和恶唑啉卤肽素类似物的合成。

  摘要：

  与海洋海绵Leiosella cf的隔离。沙门氏菌和卤代肽D（5）（以前分离的卤代肽AC（1-3）的亲戚）的结构描述以及许多恶唑啉类似物（7 ad和epi-7 cd）的总合成已得到描述。所开发的合成策略可灵活地进入卤肽的聚酮化合物结构域的各种异构体，并且在大环内酰胺化过程之后即兴地用于恶唑啉环的后期构建，从而确保了所需的大环化合物。

  DOI：

  10.1002/chem.200500624
• 作为产物：
  描述：

  (R)-3-(tert-butyldiphenylsilyloxy)-2-methylpropan-1-ol 在 吡啶 、 4-二甲氨基吡啶 、 sodium perborate tetrahydrate 、 二异丁基氢化铝 、 lithium hexamethyldisilazane 作用下， 以 四氢呋喃 、 水 为溶剂， 反应 2.0h， 生成 (4R) 5-(t-butyldiphenylsilyloxy)-4-methylpentan-1-ol
  参考文献：
  名称：

  Highly Stereocontrolled Total Synthesis of β-d-Mannosyl Phosphomycoketide: A Natural Product from Mycobacterium tuberculosis

  摘要：

  beta-D-Mannosyl phosphomycoketide (C-32-MPM), a naturally occurring glycolipid found in the cell walls of Mycobacterium tuberculosis, acts as a potent antigen to activate T-cells upon presentation by CD1c protein. The lipid portion of C-32-MPM contains, a C-32-mycoketide, consisting of a saturated oligoisoprenoid chain with five chiral methyl branches. Here we develop several stereocontrolled approaches to assemble the oligoisoprenoid chain with high stereopurity (>96%) using Julia-Kocienski olefinations followed by diimide reduction. By careful choice of olefination sites, we could derive all chirality from a single commercial compound, methyl (2S)-3-hydroxy-2-methylpropionate (>99% ee). Our approach is the first highly stereocontrolled method to prepare C-32-MPM molecule with >96% stereopurity from a single >99% ee starting material. We anticipate that our methods will facilitate the highly stereocontrolled synthesis of a variety of other natural products containing chiral oligoisoprenoid-like chains, including vitamins, phytol, insect pheromones, and archaeal lipids.

  DOI：

  10.1021/jo4006602

文献信息

• Formal total synthesis of (−)-spongidepsin
  作者：S. Chandrasekhar、S.R. Yaragorla、L. Sreelakshmi、Ch. Raji Reddy

  DOI：10.1016/j.tet.2008.03.041

  日期：2008.5

  The formal total synthesis of (−)-spongidepsin is described. Three fragments I, II, and III were first prepared from readily available starting materials and then assembled to the target compound. The key steps involved in the synthesis are asymmetric α-hydroxylation, Ender's alkylation, and ring-closing metathesis reactions. An alternative route for the fragment II is also achieved involving Sharpless

  描述了（-）-海绵蛋白酶的正式全合成。首先从容易获得的起始原料中制备三个片段I，II和III，然后组装成目标化合物。合成中涉及的关键步骤是不对称α-羟基化，Ender烷基化和闭环易位反应。还实现了片段II的替代途径，其中涉及Sharpless不对称环氧化和吉尔曼烷基化作为关键反应。
• Stereoselective formal total synthesis of the cyclodepsipeptide (−)-spongidepsin
  作者：Srivari Chandrasekhar、Srinivasa Rao Yaragorla、Lella Sreelakshmi

  DOI：10.1016/j.tetlet.2007.08.017

  日期：2007.10

  The formal total synthesis of (−)-spongidepsin is achieved starting from easily available raw materials involving asymmetric α-hydroxylation, Enders alkylation, and RCM as key reactions.

  （-）-海绵蛋白酶的正式全合成是从容易获得的原料开始的，这些原料涉及不对称的α-羟基化，Enders烷基化和RCM作为关键反应。
• Biosynthesis of tetronasin: Part 4, preparation of deuterium labelled C19-C26, C17-C26, C11-C26 and C3-C26 polyketide fragments as putative biosynthetic precursors of the ionophore antibiotic tetronasin (ICI 139603)
  作者：Geert-Jan Boons、J. Andrew Clase、Ian C. Lennon、Steven V. Ley、James Staunton

  DOI：10.1016/0040-4020(95)00201-i

  日期：1995.5

  Six deuterium labelled N-acylcysteamine polyketide derivatives (3) – (8) have been prepared as putative precursors for incorporation in studies of the biosynthesis of the ionophore antibiotic tetronasin (1). The route to these compounds was designed to be flexible and to maximise the use of common synthetic fragments.

  已制备了六种氘标记的N-酰基半胱胺聚酮化合物衍生物（3）-（8）作为推论的前体，以用于离子载体抗生素trona的生物合成研究（1）。设计这些化合物的途径应灵活并最大限度地利用常见的合成片段。
• Stereoselective synthesis of C1–C9 and C9–C17 fragments of (+)-13-deoxytedanolide
  作者：J.S. Yadav、N. Rami Reddy

  DOI：10.1016/j.tet.2010.01.023

  日期：2010.4

  An efficient and highly stereoselective asymmetric synthesis of C1-C9 and C9-C17 fragments of (+)-13-deoxytedanolide have been achieved. Utilization of desymmetrization technique to prepare the triol with five stereogenic centers, regioselective Sharpless asymmetric dillydroxylation, Evans' aldol reaction, chiral methylation, and Wittig olefination are highlights of the synthesis. (C) 2010 Published by Elsevier Ltd.
• Highly Stereocontrolled Total Synthesis of β-<scp>d</scp>-Mannosyl Phosphomycoketide: A Natural Product from <i>Mycobacterium tuberculosis</i>
  作者：Nan-Sheng Li、Louise Scharf、Erin J. Adams、Joseph A. Piccirilli

  DOI：10.1021/jo4006602

  日期：2013.6.21

  beta-D-Mannosyl phosphomycoketide (C-32-MPM), a naturally occurring glycolipid found in the cell walls of Mycobacterium tuberculosis, acts as a potent antigen to activate T-cells upon presentation by CD1c protein. The lipid portion of C-32-MPM contains, a C-32-mycoketide, consisting of a saturated oligoisoprenoid chain with five chiral methyl branches. Here we develop several stereocontrolled approaches to assemble the oligoisoprenoid chain with high stereopurity (>96%) using Julia-Kocienski olefinations followed by diimide reduction. By careful choice of olefination sites, we could derive all chirality from a single commercial compound, methyl (2S)-3-hydroxy-2-methylpropionate (>99% ee). Our approach is the first highly stereocontrolled method to prepare C-32-MPM molecule with >96% stereopurity from a single >99% ee starting material. We anticipate that our methods will facilitate the highly stereocontrolled synthesis of a variety of other natural products containing chiral oligoisoprenoid-like chains, including vitamins, phytol, insect pheromones, and archaeal lipids.