(2'S,3'S,3R,4S,5R)-1-oxo-3-O-tert-butyl(dimethyl)silyl-4-O,5-O-(2',3'-dimethoxybutane-2',3'-diyl)cyclohexane-3,4,5-triol | 433693-08-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (2'S,3'S,3R,4S,5R)-1-oxo-3-O-tert-butyl(dimethyl)silyl-4-O,5-O-(2',3'-dimethoxybutane-2',3'-diyl)cyclohexane-3,4,5-triol
• 英文别名: (2S,3S,4aR,8S,8aS)-8-{[tert-butyl(dimethyl)silyl]oxy}-2.3-dimethoxy-2,3-dimethylhexahydro-1,4-benzodioxin-6(5H)-one；(2S,3S,4aR,8R,8aS)-8-[tert-butyl(dimethyl)silyl]oxy-2,3-dimethoxy-2,3-dimethyl-5,7,8,8a-tetrahydro-4aH-benzo[b][1,4]dioxin-6-one
• CAS: 433693-08-4
• 化学式: C₁₈H₃₄O₆Si
• 分子量: 374.55
• InChiKey: BRKHCWFBNASGFN-YONAWACDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.25
• 重原子数：
  25
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.94
• 拓扑面积：
  63.2
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  (2'S,3'S,3R,4S,5R)-1-oxo-3-O-tert-butyl(dimethyl)silyl-4-O,5-O-(2',3'-dimethoxybutane-2',3'-diyl)cyclohexane-3,4,5-triol 在 双[Α,Α-双(三氟甲基)苯甲醇合]二苯硫 、 锌 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 生成 (2''S,3''S,3'R,4'S,5'R)-ethyl 2,2-difluoro-2-[3'-O-tert-butyl(dimethyl)silyl-4'-O,5'-O-(2'',3''-dimethoxybutane-2'',3''-diyl)-3',4',5'-trihydroxycyclohex-1'-en-1'-yl]acetate
  参考文献：
  名称：

  Dehydration of Quinate Derivatives: Synthesis of a Difluoromethylene Homologue of Shikimic Acid

  摘要：

  我们利用马丁硫醚 {Ph2S[OC(CF3)2Ph]2} 开发出了一种将醌酯结构转化为莽草酸结构的优化程序。在合成莽草酸的新型二氟亚甲基同系物时利用了这一程序。

  DOI：

  10.1055/s-2002-19772
• 作为产物：
  描述：

  (2'S,3'S)-methyl 3-O-tert-butyl(dimethyl)silyl-4-O,5-O-(2',3'-dimethoxybutane-2',3'-diyl)quinate 在 sodium tetrahydroborate 、 sodium periodate 作用下， 以 甲醇 为溶剂， 生成 (2'S,3'S,3R,4S,5R)-1-oxo-3-O-tert-butyl(dimethyl)silyl-4-O,5-O-(2',3'-dimethoxybutane-2',3'-diyl)cyclohexane-3,4,5-triol
  参考文献：
  名称：

  Dehydration of Quinate Derivatives: Synthesis of a Difluoromethylene Homologue of Shikimic Acid

  摘要：

  我们利用马丁硫醚 {Ph2S[OC(CF3)2Ph]2} 开发出了一种将醌酯结构转化为莽草酸结构的优化程序。在合成莽草酸的新型二氟亚甲基同系物时利用了这一程序。

  DOI：

  10.1055/s-2002-19772

文献信息

• (−)-Quinic acid: a versatile precursor for the synthesis of analogues of 2-crotonyloxymethyl-(4R,5R,6R)-4,5,6-trihydroxycyclohex-2-enone (COTC) which possess anti-tumour properties
  作者：Claire L. Arthurs、Katharine F. Lingley、Michela Piacenti、Ian J. Stratford、Tanja Tatic、Roger C. Whitehead、Natasha S. Wind

  DOI：10.1016/j.tetlet.2008.02.059

  日期：2008.4

  Syntheses of three novel analogues of the Streptomyces metabolite COTC are described, using the versatile chiral pool starting material, (−)-quinic acid. The results of bioassays of the target compounds against two lung cancer cell lines, A549 and H460, are presented.

  使用通用的手性池起始材料（-）-奎宁酸描述了链霉菌代谢产物COTC的三种新型类似物的合成。给出了针对两种肺癌细胞系A549和H460的目标化合物的生物测定结果。
• Difluorinated analogues of shikimic acid
  作者：Lovely Begum、Julian M Box、Michael G.B Drew、Laurence M Harwood、Jane L Humphreys、David J Lowes、Gareth A Morris、Perrine M Redon、Francine M Walker、Roger C Whitehead

  DOI：10.1016/s0040-4020(03)00697-5

  日期：2003.6

  Investigations into the quinate to shikimate transformation have been carried out, the results of which have been exploited in the synthesis of a novel difluoromethylene homologue of shikimic acid from (-)-quinic acid. Martin's sulfurane Ph2S[OC(CF3)(2)Ph](2)} was the reagent of choice for the key dehydration step of this synthesis. The results of investigations into the synthesis of the important natural product analogue, 6,6-difluoroshikimic acid are also reported. (C) 2003 Elsevier Science 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.
• Lithium enolates from a (−)-quinic acid-derived cyclohexanone with a β-alkoxy leaving group: regioselective preparation and evaluation of enolate stability towards β-elimination
  作者：Lynne M. Murray、Peter O’Brien、Richard J.K. Taylor、Stefan Wünnemann

  DOI：10.1016/j.tetlet.2004.01.148

  日期：2004.3

  Deprotonation of a (-)-quinic acid-derived ketone 2S,3S,4aR,8R,8aS)-8-[(tert-butyl(dimethyl)silyl)oxy]-2,3-dimethoxy-2,3-dimethylhexahydro-1,4-benzodioxin-6(5H)-one} using lithium hexamethyldisilazide (LHMDS) at -78 degreesC gave one regioisomeric enolate. The regiocontrol is governed by the axial beta-silyloxy substituent and the resulting lithium enolate is stable towards beta-elimination at temperatures up to -40 degreesC. It was found that the axial beta-silyloxy group could be conveniently eliminated using 2.1 equiv of LHMDS at 0 degreesC for 1h and that an equatorial beta-alkoxy group was much more resistant to beta-elimination. A chiral lithium amide base was used to overturn the inherent regioselectivity of ketone deprotonation with LHMDS. (C) 2004 Elsevier Ltd. All rights reserved.