((2S,3S,4aR,8aR)-2,3-Dimethoxy-2,3-dimethyl-2,3,4a,8a-tetrahydro-benzo[1,4]dioxin-6-yloxy)-trimethyl-silane | 552291-06-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: ((2S,3S,4aR,8aR)-2,3-Dimethoxy-2,3-dimethyl-2,3,4a,8a-tetrahydro-benzo[1,4]dioxin-6-yloxy)-trimethyl-silane
• 英文别名: [(2S,3S,4aR,8aR)-2,3-dimethoxy-2,3-dimethyl-4a,8a-dihydro-1,4-benzodioxin-6-yl]oxy-trimethylsilane
• CAS: 552291-06-2
• 化学式: C₁₅H₂₆O₅Si
• 分子量: 314.454
• InChiKey: BWXWQMNMRXKWKD-KBXIAJHMSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  21
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  46.2
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  ((2S,3S,4aR,8aR)-2,3-Dimethoxy-2,3-dimethyl-2,3,4a,8a-tetrahydro-benzo[1,4]dioxin-6-yloxy)-trimethyl-silane 在 Selectfluor 作用下， 以 乙腈 为溶剂， 反应 0.5h， 生成 (2'S,3'S,4R,5S,6S)-6-fluoro-4-O,5-O-(2',3'-dimethoxybutane-2',3'-diyl)-4,5-dihydroxycyclohex-2-en-1-one
  参考文献：
  名称：

  Analogues of 2-crotonyloxymethyl-(4R,5R,6R)-4,5,6-trihydroxycyclohex-2-enone (COTC) with anti-tumor properties

  摘要：

  The syntheses of three novel analogues of the naturally occurring cytotoxic agent COTC are described and the results of bioassays of the target compounds against two lung cancer cell lines are presented. (c) 2006 Published by Elsevier Ltd.

  DOI：

  10.1016/j.bmcl.2006.09.072
• 作为产物：
  描述：

  (2S,3S,4aR,6S,8R,8aR)-八氢-6,8-二羟基-2,3-二甲氧基-2,3-二甲基-1,4-苯并二氧杂环己-6-羧酸甲酯 在 sodium tetrahydroborate 、 三乙胺 、 lithium hexamethyldisilazane 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 为溶剂， 反应 8.5h， 生成 ((2S,3S,4aR,8aR)-2,3-Dimethoxy-2,3-dimethyl-2,3,4a,8a-tetrahydro-benzo[1,4]dioxin-6-yloxy)-trimethyl-silane
  参考文献：
  名称：

  B-seco柠檬苦素骨架的合成。

  摘要：

  使用爱尔兰-克莱森重排作为关键转化合成了B-seco柠檬苦素类化合物的潜在立体化学复杂且功能密集的支架。

  DOI：

  10.1039/c1cc11388g

文献信息

• Total Synthesis of Branimycin: An Evolutionary Approach
  作者：Valentin S. Enev、Wolfgang Felzmann、Alexey Gromov、Stefan Marchart、Johann Mulzer

  DOI：10.1002/chem.201200257

  日期：2012.7.27

  The first total synthesis of the macrolactone antibiotic branimycin (4) has been described. The key disconnection leads to a cis‐dehydrodecalone core and a polyketide side chain which are connected via organometallic addition. The dehydrodecalone core was targeted via altogether five different approaches featuring various kinds of chiral elements and ring‐closing methodology. In the end the most successful

  已经描述了大内酯抗生素布雷尼霉素的首次全合成（4）。关键的分离导致顺式-脱氢十氢萘酮核和聚酮化物侧链，它们通过有机金属加成连接。十氢癸酮核心通过总共五种不同的方法作为目标，这些方法具有各种手性元素和闭环方法。最后，选择了最成功的方法，从二环氧萘109开始进行合成。因此，通过有机金属脱对称反应引入氧官能团和碳附件，以生成环氧乙烷107，乙烯基碘化物11在环氧乙烷107上生成。转化成有机锂物质后加入有机硅。通过经由迈克尔加成和随后的大内酯化引入酯侧链来完成合成。
• <i>cis</i>-Decalins from Quinic Acid:  Toward a Synthesis of Branimycin
  作者：Stefan Marchart、Johann Mulzer、Valentin S. Enev

  DOI：10.1021/ol0630189

  日期：2007.3.1

  [reaction: see text] Starting from (-)-quinic acid an efficient synthesis of highly functionalized cis-alpha,beta-unsaturated ketone 3, an advanced precursor of branimycin, has been accomplished via two key step reactions: a ring closing metathesis reaction to prepare the cis-decalin system, and a highly stereoselective epoxidation reaction.

  [反应：请参阅文本]从（-）-奎尼酸开始，已通过两个关键步骤反应有效合成了高度官能化的顺式α，β-不饱和酮3（布雷尼霉素的先进前体）。制备顺式十氢化萘系统和高度立体选择性的环氧化反应。
• Stereoselective Reactions of a (−)-Quinic Acid-Derived Enone:  Application to the Synthesis of the Core of Scyphostatin
  作者：Lynne M. Murray、Peter O'Brien、Richard J. K. Taylor

  DOI：10.1021/ol034521d

  日期：2003.5.1

  protected as a 2,3-dimethoxybutanediyldioxy ketal, provides an excellent template for further highly stereoselective elaboration as exemplified by its conversion into the core of scyphostatin, a potent inhibitor of neutral sphingomyelinase.

  [反应：参见正文]由（-）-奎宁酸衍生的烯酮，其反式1,2-二醇被保护为2,3-二甲氧基丁烷二基二氧基缩酮，为进一步高度立体选择性的修饰提供了极好的模板，如其转化所举例说明的进入鞘磷脂抑制素的核心位置，鞘磷脂抑制素是一种有效的中性鞘磷脂酶抑制剂。
• Stereocontrolled formation of highly substituted cis-decalins via INOC annulation. An access to the branimycin core
  作者：Valentin S. Enev、Martina Drescher、Johann Mulzer

  DOI：10.1016/j.tet.2007.02.126

  日期：2007.6

  Quinic acid was used as a chiral scaffold for elaborating the highly substituted cis-decalin core system of branimycin via an Eschenmoser-Ireland rearrangement-INOC annulation sequence. (C) 2007 Elsevier Ltd. All rights reserved.
• The synthesis of 2-oxyalkyl-cyclohex-2-enones, related to the bioactive natural products COTC and antheminone A, which possess anti-tumour properties
  作者：Claire L. Arthurs、Gareth A. Morris、Michela Piacenti、Robin G. Pritchard、Ian J. Stratford、Tanja Tatic、Roger C. Whitehead、Katharine F. Williams、Natasha S. Wind

  DOI：10.1016/j.tet.2010.08.072

  日期：2010.11

  The syntheses of five novel 2-oxyalkyl-cyclohex-2-enones, structurally related to the natural products COTC and antheminone A. are described. The target structures were selected in order to probe the influence of several key structural parameters on in vitro anti-cancer bioactivity. The results of a cytotoxicity bioassay of the compounds against non-small-cell lung cancer cell lines A549 and H460 are reported. The biological data provides useful information, which will help guide the future design of compounds in this class with enhanced anti-cancer activity. (C) 2010 Elsevier Ltd. All rights reserved.