3,4-O-isopropylidene-L-(S)-erythrulose | 115114-86-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 3,4-O-isopropylidene-L-(S)-erythrulose
• 英文别名: erythrulose 3,4-acetonide；L-(S)-3,4-O-isopropylideneerythrulose；(S)-1-(2,2-Dimethyl-1,3-dioxolan-4-yl)-2-hydroxyethanone；1-[(4S)-2,2-dimethyl-1,3-dioxolan-4-yl]-2-hydroxyethanone
• CAS: 115114-86-8
• 化学式: C₇H₁₂O₄
• 分子量: 160.17
• InChiKey: UDEWEEBHLHMAOR-LURJTMIESA-N

物化性质

• 沸点：
  248.4±40.0 °C(Predicted)
• 密度：
  1.160±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  -0.4
• 重原子数：
  11
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.86
• 拓扑面积：
  55.8
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  3,4-O-isopropylidene-L-(S)-erythrulose 在 sodium tetrahydroborate 作用下， 以 甲醇 、 异丙醇 为溶剂， 反应 3.17h， 生成 (R)-4-(2-羟乙基)-2,2-二甲基-1,3-二氧戊环
  参考文献：
  名称：

  L-（S）-赤藓糖：（R）-1,2,4-丁三醇和一些相关的C 4 ron的合成。

  摘要：

  L-（S）-赤藓糖可轻松转化为（R）-1,2,4-丁三醇和相关的C 4手性结构单元。提出了（-）GABOB的形式合成。还描述了3-亚甲基-1,2,4-丁三醇衍生物的形成。

  DOI：

  10.1016/s0040-4039(00)96619-x
• 作为产物：
  描述：

  L(+)-赤藓酮糖(水合) 、 丙酮 在 sodium sulfate 、 zinc(II) chloride 作用下， 以 1,4-二氧六环 、 甲醇 为溶剂， 反应 15.0h， 以81%的产率得到3,4-O-isopropylidene-L-(S)-erythrulose
  参考文献：
  名称：

  L-（S）-赤藓糖L-2,3-O-异亚丙基-C 3螯合物的新型前体

  摘要：

  从现在大量可用的L-（S）-赤藓糖开始，通过受保护的L-描述了（S）-3，4-O-异亚丙基亚紫苏糖。

  DOI：

  10.1016/s0040-4039(00)96618-8

文献信息

• Stereoselective 1,3-Dipolar Cycloadditions of a Chiral Nitrone Derived from Erythrulose. An Experimental and DFT Theoretical Study
  作者：Miguel Carda、Raul Portolés、Juan Murga、Santiago Uriel、J. Alberto Marco、Luis R. Domingo、Ramón J. Zaragozá、Harald Röper

  DOI：10.1021/jo0009651

  日期：2000.10.1

  chosen as computational models. The cycloadditions have been shown to take place through one-step pathways in which the C-C and C-O sigma bonds are formed in a nonsynchronous way. For the reaction with methyl propiolate, DFT calculations predict the experimentally observed meta regioselectivity. For the reaction with acrylonitrile, however, the predicted regioselectivity has been found to depend on the

  我们研究了由L-赤藓糖制备的手性硝酮的几个1,3-偶极环加成反应。虽然双极性亲和剂如丙烯酸乙酯，丙酸乙酯或乙炔二甲酸二甲酯的碳-碳多键的环加成的立体选择性较差，但与丙烯腈的反应主要提供了一种非对映异构体加合物。此外，发现两种结构相似的双极性亲和剂丙烯酸乙酯和丙酸乙酯表现出的区域选择性相反。因此，已经通过具有B3LYP功能以及6-31G和6-31 + G基组的密度泛函理论（DFT）方法研究了这些环加成的分子机理。选择简化的非手性形式的硝酮1作为偶极子，丙酸甲酯或丙烯腈作为偶极子，作为计算模型。环加成反应已显示为一步一步发生，其中CC和CO sigma键以非同步方式形成。对于与丙酸甲酯的反应，DFT计算可预测实验观察到的间位选择性。然而，对于与丙烯腈的反应，已经发现预测的区域选择性取决于所用的计算水平。计算结果进一步表明，在后一种偶极亲子的情况下，exo方法应得到大力支持，与实验结果相符。造成
• Diastereoselective additions of organolithium and organomagnesium reagents to the CN bond of a chiral, cyclic nitrone derived from erythrulose
  作者：J.Alberto Marco、Miguel Carda、Juan Murga、Raul Portolés、Eva Falomir、Johann Lex

  DOI：10.1016/s0040-4039(98)00400-6

  日期：1998.5

  The reaction of the 3,4-O-isopropylidene-l-(S)-erythrulose with hydroxylamine, followed by treatment of the resulting mixture of (E)- and (Z)-oximes with acetone and an acid catalyst, afforded two crystalline chiral compounds. Through X-ray diffraction analysis, these products were identified as a double acetonide derived from the (E)-oxime and a cyclic nitrone derived from the (Z)-oxime. The additions

  3，4-O-异亚丙基-1-（S）-赤藓糖与羟胺反应，然后用丙酮和酸催化剂处理所得的（E）-和（Z）-肟的混合物，得到两种结晶手性化合物。通过X射线衍射分析，将这些产物鉴定为衍生自（E）-肟的双丙酮化物和衍生自（Z）-肟的环状硝酮。发现将有机锂和有机镁试剂加到硝酮的CN键上是非对映选择性的。加成产物是有用的中间体，用于制备对映纯形式的α，α-二取代的α-氨基酸和其他含氮化合物。
• Diastereoselective conversion of L-(S)-erythrulose to 2-amino-2-deoxy-L-erythritol
  作者：Elisabeth Dequeker、Frans Compernolle、Suzanne Toppet、Georges Hoornaert

  DOI：10.1016/0040-4020(95)00239-5

  日期：1995.5

  L-(S)-Erythrulose (1) was converted into 2-amino-2-deoxy-L-erythritol (2) (six steps, overall yield 35%) through diastereoselective reduction of the bridged orthoester 21, (1S,5S)-2,7,8-trioxabicyclo[3.2.1]octan-4-one-O-benzyloxime, with K-selectride® as the key process. Alternative methods, involving reduction of the imino group in acyclic O-benzyloxime derivatives of 1, or reductive amination of

  L-（S）-Erythrulose（1）转化为2-氨基-2-脱氧-L-赤藓醇（2通过非对映选择性还原的桥连原酸酯）（六个步骤，总产率35％）21，（1S，5S） -2,7,8-三氧杂双环[3.2.1] octan-4-one- O-苄基肟，关键过程为K-selectride®。替代方法涉及还原1的无环O-苄基肟衍生物中的亚氨基，或2-酮官能团的还原胺化，得到不同比例的赤和苏2-氨基非对映异构体。脱保护的铵盐的旋转异构体的分布显然是由铵基团和3-羟基氧之间的氢键控制的，从而产生特征性的3 J H-2，H-3耦合常数。通过α-亚甲基位置的去质子化取代桥连的O-苄基肟21和22是不成功的。
• Reaction of Superoxide with Ascorbic Acid Derivatives: Insight into the Superoxide-Mediated Oxidation of Dehydroascorbic Acid
  作者：Aryeh A. Frimer、Pessia Gilinsky-Sharon

  DOI：10.1021/jo00114a031

  日期：1995.5

  In order to gain greater insight into the mechanism of superoxide-mediated oxidation of ascorbic acid (1) in aprotic media, we reacted O-2(.-) (generated from KO2/18-crown-6 in toluene) with vitamin C derivatives 13a and 14a and the corresponding mono- and dimethoxy analogs 13b and 13c, respectively. Dihydroxyfuranones 13a and 14a underwent oxidative cleavage with O-2(.-) yielding, upon methyl iodide workup, the corresponding keto ester (15 or 17, respectively) and threonic acid analog (16 or 18, respectively). On the other hand, mono- and dimethoxy analogs 13b and 13c each react with superoxide to give a single isolable product, oxyester 16 and alkylidenefuranone 20, respectively. Finally, 13a reacts with tert-butoxide, again yielding 16 as the major product. The data are best resolved by suggesting that ascorbic acid analogs 13a and 14a (and presumably ascorbic acid as well) are oxidized by O-2(.-) to the corresponding triketone 21 which reacts in turn by attack at the highly electrophilic central carbonyl C-2. Cyclization of the resulting 2-peroxy 1,3-diketone 22 into the C-1 carbonyl, followed by oxidative cleavage, saponification, and methylation, yields the observed products. By contrast, O-2(.-) oxidation of 13b and tert-butoxide oxidation of 13a yield 3-peroxy-1,2-diketone 29 which cyclizes into the C-1 carbonyl ultimately yielding 16. Finally, 13c, which lacks enolic hydrogens, undergoes abstraction of the gamma-hydrogen followed by the elimination of acetone, yielding 20. Similarly, 5,6-dihydropyrone 33 undergoes superoxide-mediated elimination yielding dienone 34. The data presented herein are consistent with the mechanism suggested by Sawyer et al. (J. Am. Chem. Sec. 1982, 104, 6273-6278) for the superoxide-mediated oxidation of dehydroascorbic acid (2)-with the modification that the position of initial O-2(.-) attack is at the C-2 (rather than the C-3) carbonyl.
• Bacterial sterol surrogates. Determination of the absolute configuration of bacteriohopanetetrol side chain by hemisynthesis of its diastereoisomers
  作者：Philippe Bisseret、Michel Rohmer

  DOI：10.1021/jo00273a034

  日期：1989.6