diethyl (-)-(4S,5S)-4,5-O-isopropylidene-4,5-dihydroxy-2,6-octadienedioate | 115237-15-5

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: diethyl (-)-(4S,5S)-4,5-O-isopropylidene-4,5-dihydroxy-2,6-octadienedioate
• 英文别名: diethyl (4R,5R)-4,5-O-isopropylidene-2(E),6(E)-octadiendioate；ethyl (E)-3-[(4S,5S)-5-[(E)-3-ethoxy-3-oxoprop-1-enyl]-2,2-dimethyl-1,3-dioxolan-4-yl]prop-2-enoate
• CAS: 115237-15-5
• 化学式: C₁₅H₂₂O₆
• 分子量: 298.336
• InChiKey: KFNPAMUWPYXWQY-KEXQNEGFSA-N

物化性质

• 沸点：
  397.6±37.0 °C(predicted)
• 密度：
  1.174±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  21
• 可旋转键数：
  8
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  71.1
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  diethyl (-)-(4S,5S)-4,5-O-isopropylidene-4,5-dihydroxy-2,6-octadienedioate 在 盐酸 、 4-二甲氨基吡啶 作用下， 以 乙醇 、 二氯甲烷 为溶剂， 反应 4.0h， 生成 Diethyl (4S,5S)-4,5-bis(cinnamoyloxy)-2E,6E-octadienedioate
  参考文献：
  名称：

  Conformational diagnosis of diethyl (4S,5S)-4,5-bis(tert-butyldimethylsiloxy)-2E,6E-octadienedioate based on the stereochemical outcomes of representative reactions as compared with those of its 4,5-O-isopropylidene derivatives and on a dichroic exciton chirality method

  摘要：

  In order to gain more insight into the conformation of diethyl (4S,5S)-4,5-bis(tert-butyldimethylsiloxy)-2E,6E-octadienedioate (1) experimentally, some appropriate reactions of 1 and its derivative (S,S)-3, which bears isopropylidene protecting groups, have been executed. The stereochemical outcomes of such reactions as the Diels-Alder reaction, osmium tetraoxide-catalyzed hydroxylation, conjugate addition with amines, and cyclopropanation with phosphonium ylides point to a rigid conformation (1A) in which the vicinal TBDMSO groups, the most bulky substituents, are arranged in an anti relationship, and, therefore, the enoate groups are forced to be gauche each other. A dichroic exciton chirality study has also provided clear-cut evidence for this rigid conformation.

  DOI：

  10.1021/jo00075a024
• 作为产物：
  描述：

  diisopropyl (2S,3S)-2,3-O-isopropylidenetartrate 在 二异丁基氢化铝 作用下， 以 四氢呋喃 、 正己烷 、 甲苯 为溶剂， 反应 6.5h， 生成 diethyl (-)-(4S,5S)-4,5-O-isopropylidene-4,5-dihydroxy-2,6-octadienedioate
  参考文献：
  名称：

  Synthesis of axially dissymmetric 3,5-octadiene framework with C2 chirality via palladium(II)-catalyzed twofold [3,3]sigmatropic rearrangement

  摘要：

  DOI：

  10.1016/s0040-4039(00)86676-9

文献信息

• Synthesis of chiral 3E,5E-octadiene-1,2R,7R,8-tetraol frameworks by means of palladium(II)-promoted hetero-Claisen rearrangement: Mechanistic aspect
  作者：Seiki Saito、Akiyoshi Kuroda、Hiroshi Matsunaga、Shushiro Ikeda

  DOI：10.1016/0040-4020(96)00854-x

  日期：1996.10

  for the exclusive formation of symmetrical dienediol such as 1,6-bis(acetoxy)-2,4-diene in palladium(II)-promoted [3,3]sigmatropic rearrangement of 3,4-bis(acetoxy)-1,5-diene system. This mechanism referred to as migration-induced intramolecular dioxanium ion switching (MIDIS) process can reasonably explain why the vicinal acetoxy groups move from 3,4-position not to 5,6- but two-directionally to 1

  已经提出了一种可能的机理，用于在钯（II）促进的3,4-双（3,3）σ重排中独家形成对称的二烯二醇，例如1,6-双（乙酰氧基）-2,4-二烯。乙酰氧基）-1,5-二烯体系。这种被称为迁移诱导的分子内二恶烷离子交换（MIDIS）过程的机制可以合理地解释为什么邻位乙酰氧基不是从3,4-位置移动到5,6-而是从两个方向移动到1,6-位置。
• A Facile Access to Enantiomerically Pure [60]Fullerene Bisadducts with the Inherently Chiral <i>Trans</i>-3 Addition Pattern
  作者：Maria Riala、Nikos Chronakis

  DOI：10.1021/ol200816z

  日期：2011.6.3

  acetonide moieties led to the synthesis and successful column chromatographic isolation of the enantiomerically pure f,sC and f,sA bisadducts with the inherently chiral trans-3 addition pattern. Acidic deprotection of the acetonide groups gave access to novel chiral fullerene compounds which combine the inherent chirality of the fullerene core with the functional glycol groups located on the tether.

  C 60与对映体纯的双丙二酸酯系链与两个丙酮酸酯部分之间的Bingel反应导致对映体纯的f，s C和f，s A双加合物具有固有的手性反式-3加成模式，从而合成并成功进行了柱色谱分离。乙醛酸基团的酸性脱保护得到了新颖的手性富勒烯化合物，该化合物将富勒烯核的固有手性与位于系链上的官能二醇基团结合在一起。
• Concurrent reductive cleavage and recombination of γ,δ-alkylidenedioxy-α,β-unsaturated esters promoted by organocuprates
  作者：Seiichi Takano、Yoshinori Sekiguchi、Kunio Ogasawara

  DOI：10.1039/c39880000449

  日期：——

  Treatment of γ,β-alkylidenedioxy-α,β-unsaturated esters (1) with lithium dimethylcuprate furnishes β′δ-dihydroxy-β,γ-unsaturated esters (2) in moderate to good yields by concurrent reductive cleavage to ketones (5) and enolates (6) and their aldolic recombination.

  用二甲基碳酸铜锂处理γ，β-亚烷基二氧基-α，β-不饱和酯（1）通过同时还原性裂解为酮（5），以中等至良好的产率提供β'δ-二羟基-β，γ-不饱和酯（2）。和烯醇化（6）及其醛醇重组。
• A regio-, (E)-stereo-, and chemo-selective synthesis of unsymmetrical divinylmethanols starting from L- and D-tartrates via organocyanocopper Lewis acid mediated 1,3-chirality transfer
  作者：Toshiro Ibuka、Miwa Tanaka、Yoshinori Yamamoto

  DOI：10.1039/c39890000967

  日期：——

  A regio-, (E)-stereo-, and chemo-selective synthesis of synthetically useful unsymmetrical divinylmethanol derivatives, compounds that are not easily accessible by other means, via an organocyanocopper·BF3 mediated 1,3-chirality transfer in mixed solvents involving tetrahydrofuran at –78 °C is reported.

  合成有用的不对称二乙烯基甲醇衍生物的区域，（E）-立体和化学选择性合成，这些化合物不易通过其他方式通过有机氰铜·BF 3介导的在混合溶剂中的1,3-手性转移而通过其他方式获得据报道，四氢呋喃在–78°C下。
• <i>Syn</i>-Selective Michael Addition of Amines to Bis-Enones:  Synthesis of 1,3,4,7-Tetrasubstituted (4<i>R</i>,5<i>S</i>,6<i>S</i>,7<i>R</i>)-Hexahydro-5,6-dihydroxy-2<i>H</i>-1,3-diazepin-2-ones
  作者：Erwin P. Schreiner、Arno Pruckner

  DOI：10.1021/jo970384k

  日期：1997.8.1

  O-protected 1,3,4,7-tetrasubstituted (4R,5S,6S,7R)-hexahydro-5,6-dihydroxy-2H-1,3-diazepin-2-ones 7a-d are seven-membered cyclic ureas useful as intermediates in the synthesis of HIV-proteinase inhibitors. We succeeded in preparing them using a three-step sequence starting from diethyl isopropylidene-L-tartrate 1. In a one-pot reaction 1 was transformed via an in situ generated aldehyde and subsequent Wittig reaction into the bis-enones 2a,b. Treatment with excess of primary amines resulted in a two-fold syn-selective Michael addition at low temperature that generated predominantly the C-2-symmetric 1,4-bis(aminoalkyl) derivatives 3a-d. Here we investigated the influence of reaction temperature and configuration of the starting bis-olefin on stereoselectivity. The cyclic ureas 6a-d were formed by treatment of 3a-d with phosgene at elevated temperature. We succeeded in extending this approach to asymmetric substituted cyclic ureas by controlled monoaddition of benzylamine to 2a, providing the monoaddition product 5a in good yields. Finally, conjugate addition of a second amine to 5a followed by cyclization gave the pseudo-C-2-symmetric cyclic urea 9.