(2'S,3'S)-methyl 3-O-tert-butyl(dimethyl)silyl-4-O,5-O-(2',3'-dimethoxybutane-2',3'-diyl)quinate | 213536-05-1

• 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)-methyl 3-O-tert-butyl(dimethyl)silyl-4-O,5-O-(2',3'-dimethoxybutane-2',3'-diyl)quinate
• 英文别名: methyl (2'S,3'S)-5-O-tert-butyldimethylsilyl-3-O,4-O-(2',3'-dimethoxybutane-2',3'-diyl)quinate；methyl (2'S,3'S)-5-O-t-butyldimethylsilyl-3-O,4-O-(2',3'-dimethoxybutane-2',3'-diyl)quinate；methyl (2S,3S,4aR,6R,8R,8aS)-8-[tert-butyl(dimethyl)silyl]oxy-6-hydroxy-2,3-dimethoxy-2,3-dimethyl-5,7,8,8a-tetrahydro-4aH-benzo[b][1,4]dioxine-6-carboxylate
• CAS: 213536-05-1
• 化学式: C₂₀H₃₈O₈Si
• 分子量: 434.602
• InChiKey: ULVQQXNURPYDAZ-DBRQCVRVSA-N

物化性质

• 熔点：
  114-115 °C
• 沸点：
  444.8±45.0 °C(Predicted)
• 密度：
  1.11±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.58
• 重原子数：
  29
• 可旋转键数：
  7
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.95
• 拓扑面积：
  92.7
• 氢给体数：
  1
• 氢受体数：
  8

反应信息

• 作为反应物：
  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 2,6-二甲基吡啶 、 sodium chlorite 、 2-甲基-2-丁烯 、 三丁基膦 、 二异丁基氢化铝 、 间氯过氧苯甲酸 、 三氟乙酸 、 三氟乙酸酐 作用下， 以 四氢呋喃 、 水 、 叔丁醇 为溶剂， 生成 莽草酸
  参考文献：
  名称：

  Direct conversion of 1,2-diol into allyl sulfide. Regioselective transformation of (−)-quinic acid to (−)-shikimic acid

  摘要：

  Exo-1,2-diols 3 and 4 were efficiently converted into the corresponding allyl sulfides by means of tri-n-butylphosphine (Bu3P) and diphenyl disulfide (PhS)(2). This method was applied to the introduction of a carbon-carbon double bond from diol 11 to give allyl sulfide 12 in a highly regioselective manner. The allyl sulfide 12 was transformed into (-)-shikimic acid (1) in four steps. (C) 1998 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(98)01239-8
• 作为产物：
  描述：

  methyl 6,8-dihydroxy-2,3-dimethoxy-2,3-dimethyl-5,7,8,8a-tetrahydro-4aH-benzo[b][1,4]dioxine-6-carboxylate 以98的产率得到(2'S,3'S)-methyl 3-O-tert-butyl(dimethyl)silyl-4-O,5-O-(2',3'-dimethoxybutane-2',3'-diyl)quinate
  参考文献：
  名称：

  Tetrahedron 2015, 71, 3120-3130

  摘要：

  DOI：

文献信息

• Efficient and versatile synthesis of 5-O-acylquinic acids with a direct esterification using a p-methoxybenzyl quinate as a key intermediate
  作者：Kin-ichi Oyama、Noriyuki Watanabe、Tomomi Yamada、Masako Suzuki、Yukiko Sekiguchi、Tadao Kondo、Kumi Yoshida

  DOI：10.1016/j.tet.2014.08.064

  日期：2015.5

  An efficient and versatile synthesis of 5-O-acylquinic acids from commercially available (−)-quinic acid was accomplished. We designed p-methoxybenzyl quinate as a key intermediate, and two problems, the esterification of the sterically hindered 5-OH group for the concise divergent synthesis and the low yield of the final deprotection step, were solved. For the first problem, we improved Tanabe's method

  从市售（-）-奎宁酸完成了5- O-酰基奎宁酸的有效和通用合成。我们设计了对甲氧基苄基奎宁酸酯作为关键中间体，并解决了两个问题，即空间位阻的5-OH基团的酯化，以实现简洁的发散合成和最终脱保护步骤的收率低。对于第一个问题，我们通过添加i -Pr 2 NEt改进了田边的方法，即使用游离羧酸的TsCl / NMI介导的酯化反应。对于第二个问题，我们为最终的脱保护步骤建立了TFA或BCl 3 / C 6 HMe 5催化的脱保护反应。5 Ø-酰基奎尼酸通过七个步骤合成，总收率为45-60％。
• Dehydration of Quinate Derivatives: Synthesis of a Difluoromethylene Homologue of Shikimic Acid
  作者：Julian M. Box、Laurence M. Harwood、Jane L. Humphreys、Gareth A. Morris、Perrine M. Redon、Roger C. Whitehead

  DOI：10.1055/s-2002-19772

  日期：——

  An optimised procedure for the conversion of a quinate to shikimate structure has been developed using Martin"s Sulfurane Ph2S[OC(CF3)2Ph]2}. This protocol has been exploited in the synthesis of a novel difluoromethylene homologue of shikimic acid.

  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。
• 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.
• Synthesis of Designed Acylquinic Acid Derivatives Involved in Blue Color Development of Hydrangea and Their Co-pigmentation Effect
  作者：Kumi Yoshida、Yuki Toyama-Kato、Tadao Kondo

  DOI：10.3987/com-06-s(k)6

  日期：——
• Essential structure of co-pigment for blue sepal-color development of hydrangea
  作者：Tadao Kondo、Yuki Toyama-Kato、Kumi Yoshida

  DOI：10.1016/j.tetlet.2005.07.146

  日期：2005.9

  Blue sepal-color of Hydrangea macrophylla might be due to a supramolecular metal-complex pigment consisting of delphinidin 3-glucoside (1), co-pigments (5-O-caffeoylquinic acid (2), and/or 5-O-p-coumaroylquinic acid (3)) and Al3+ in an aqueous solution around pH 4.0. To clarify the mechanism of blue sepal-color development of hydrangea, we tried to reproduce the blue color in vitro by mixing 1 with designed synthetic co-pigments in the presence of Al3+ at pH 4.0. We at first succeeded in clarifying the essential functional structure in the co-pigment that could form the stable blue solution. Here, we present the structure of the blue pigment caused by an Al-complex coordinating of I at ortho-dihydroxyl groups of the B-ring, 1-hydroxy, 1-carboxylic acid, and the carbonyl residue in the ester at 5-position of 2 and/or 3. The hydrophobic interaction between the aromatic acyl residue at 5-position and the nucleus of 1 may also contribute to stabilize the complex. (c) 2005 Elsevier Ltd. All rights reserved.