diethyl-2,3-O-benzylidene-D-tartrate

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: diethyl-2,3-O-benzylidene-D-tartrate
• 英文别名: diethyl (4R,5S)-2-phenyl-1,3-dioxolane-4,5-dicarboxylate
• 化学式: C₁₅H₁₈O₆
• 分子量: 294.304
• InChiKey: BAMBLLDJYZVARV-ODOQXGPZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  21
• 可旋转键数：
  7
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.47
• 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-2,3-O-benzylidene-D-tartrate 在 lithium aluminium tetrahydride 、 三氯化铝 、 对甲苯磺酸 作用下， 以 乙醚 、 二氯甲烷 为溶剂， 生成 2-O-benzyl-3,4-O-isopropylidene-L-threitol
  参考文献：
  名称：

  A convergent total synthesis of (+)-anamarine from (R,R)-tartrate and D-gulonolactone

  摘要：

  DOI：

  10.1016/s0040-4039(00)96881-3
• 作为产物：
  描述：

  L-(+)-酒石酸二乙酯 、 苯甲醛 在 对甲苯磺酸 作用下， 以 苯 为溶剂， 以89%的产率得到diethyl-2,3-O-benzylidene-D-tartrate
  参考文献：
  名称：

  A convergent total synthesis of (+)-anamarine from (R,R)-tartrate and D-gulonolactone

  摘要：

  DOI：

  10.1016/s0040-4039(00)96881-3

文献信息

• A highly efficient, enantioselective and recyclable mesoporous silica-based Mn(<scp>ii</scp>) catalyst for asymmetric oxidation of thioanisole
  作者：Sohaila Alavi、Hassan Hosseini-Monfared、Pavlo Aleshkevych

  DOI：10.1039/c4ra07256a

  日期：——

  The development of environmentally benign reactions is an important goal in synthetic organic chemistry and chemical engineering. However, catalytic enantioselective oxidations using transition-metal complexes are limited when the oxidant is hydrogen peroxide. A hydrazone based asymmetric ligand (H2L) was used to prepare a heterogeneous catalyst by the immobilization of its manganese complex, [Mn(H2O)2Cl2}2(H2Btar)] (1), on mesoporous support SBA-15 via the post grafting method (H2L = 2,3-O-4-hydroxybenzhydrazidebenzylidene-D-tartrate). The heterogeneous asymmetric catalyst 1-SBA15 was characterized by elemental analysis; small angle X-ray diffraction (SAX), scanning electron microscopy (SEM), nitrogen sorption measurement, Fourier transform infrared spectroscopy and EPR spectroscopy. The asymmetric oxidation of thioanisole (PhSMe) was achieved with hydrogen peroxide in the presence of 1-SBA15 in excellent conversion and enantioselectivity (>99% ee). Compared to a homogeneous catalyst, the heterogenized catalyst is more stable and can be recycled four times without any significant loss of activity. Immobilization of complex 1 onto SBA-15 increased the selectivity toward sulfone in the oxidation.

  开发对环境无害的反应是合成有机化学和化学工程的一个重要目标。然而，当氧化剂为过氧化氢时，使用过渡金属配合物催化对映体选择性氧化受到限制。通过后接枝法（H2L = 2,3-O-4-羟基苯肼亚苄基-D-酒石酸盐）将其锰配合物[Mn(H2O)2Cl2}2(H2Btar)] (1)固定在介孔载体 SBA-15 上，利用一种基于腙的不对称配体（H2L）制备了一种异相催化剂。通过元素分析、小角 X 射线衍射（SAX）、扫描电子显微镜（SEM）、氮吸附测量、傅立叶变换红外光谱和 EPR 光谱对异相不对称催化剂 1-SBA15 进行了表征。在 1-SBA15 的存在下，用过氧化氢实现了硫代苯甲醚（PhSMe）的不对称氧化，具有极佳的转化率和对映体选择性（>99% ee）。与均相催化剂相比，异质化催化剂更加稳定，可以循环使用四次而不会明显丧失活性。将复合物 1 固定在 SBA-15 上提高了氧化过程中对砜的选择性。
• A convergent total synthesis of (+)-anamarine from (R,R)-tartrate and D-gulonolactone
  作者：Klaus Lorenz、Frieder W. Lichtenthaler

  DOI：10.1016/s0040-4039(00)96881-3

  日期：1987.1
• Visible Light Initiated Photosensitized Electron Transfer Cyclizations of Aldehydes and Ketones to Tethered α,β-Unsaturated Esters:  Stereoselective Synthesis of Optically Pure <i>C</i>-Furanosides
  作者：Ganesh Pandey、Saumen Hajra、Manas K. Ghorai、K. Ravi Kumar

  DOI：10.1021/jo9702812

  日期：1997.8.1

  Photosensitized one-electron reductive activation of aldehydes/ketones tethered with activated olefins leads to efficient cyclization to give diastereoselective cycloalkanols in high yield. The activation is promoted by secondary and dark electron transfer from visible light (405 nm) initiated photosensitized electron transfer generated 9,10-dicyanoanthracene radical anion (DCA(.-)). The DCA(.-) is produced by electron transfer using either triphenylphosphine (Ph3P) as sacrificial electron donor (PS-A) or 1,5-dimethoxynaphthalene (DMN) as primary electron donor and ascorbic acid as sacrificial electron donor (PS-B), to light-absorbing DCA. The cyclization is suggested to involve ketyl radical intermediate. High trans diastereoselectivity is observed during the formation of cycloalkanols. This cyclization strategy is further extended for the stereoselective synthesis of optically pure C-furanoside (41), starting from naturally occuring L-tartaric acid. The stereochemistry of 41 is suggested based on the single-crystal X-ray diffraction data.