methyl 4,6-O-(R)-benzylidene-2-O-methyl-α-D-ribohexopyranosid-3-ulose | 88390-61-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡喃二恶英
• 英文名称: methyl 4,6-O-(R)-benzylidene-2-O-methyl-α-D-ribohexopyranosid-3-ulose
• 英文别名: methyl 4,6-O-benzylidene-2-O-methyl-α-D-arabino-hexopyranosid-3-ulose；methyl 4,6-O-benzylidene-2-O-methyl-α-D-ribo-hexopyranosid-3-ulose；methyl 4,6-O-benzyliden-2-O-methyl-α-D-ribo-hexopyranosid-3-ulose；(2R,4aR,6S,7S,8aR)-6,7-dimethoxy-2-phenyl-4a,6,7,8a-tetrahydro-4H-pyrano[3,2-d][1,3]dioxin-8-one
• CAS: 88390-61-8
• 化学式: C₁₅H₁₈O₆
• 分子量: 294.304
• InChiKey: WZULTIRVGOJYJD-GZENYHORSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.8
• 重原子数：
  21
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.53
• 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：

  methyl 4,6-O-(R)-benzylidene-2-O-methyl-α-D-ribohexopyranosid-3-ulose 在 四丁基氢氧化铵 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 反应 0.16h， 生成 (2R,4aR,6S,7R,8R,8aR)-8-Hydroxy-6,7-dimethoxy-2-phenyl-hexahydro-pyrano[3,2-d][1,3]dioxine-8-carbaldehyde
  参考文献：
  名称：

  由羰基化合物合成2-氯醛并将其转化为2-羟醛衍生物的新方法

  摘要：

  由羰基化合物与[氯甲基（二甲基）ulf三氟甲烷磺酸盐（1）]和DBU在THF中以高收率合成了2-氯醛衍生物。此外，通过用n- Bu 4 NOH以高产率和反相构型处理衍生物，将2-氯醛衍生物转化为相应的2-羟基醛。所有产物的立体化学通过NMR（NOE）测定。

  DOI：

  10.1016/s0040-4039(01)00522-6
• 作为产物：
  描述：

  methyl 2,3-anhydro-4,6-benzylidene-α-D-allopyranoside 在 三乙胺 、 pyridinium chlorochromate 作用下， 以 甲醇 、 乙醇 、 二氯甲烷 为溶剂， 反应 5.0h， 生成 methyl 4,6-O-(R)-benzylidene-2-O-methyl-α-D-ribohexopyranosid-3-ulose
  参考文献：
  名称：

  New mannose-derived ketones as organocatalysts for enantioselective dioxirane-mediated epoxidation of arylalkenes. Part 3: Chiral ketones from sugars

  摘要：

  New D-arabino-hexopyranosid-3-uloses were synthesized by a simple method from mannopyranoside derivatives. The common skeleton possesses a tunable alkoxy group as steric sensor on carbon 2 of the sugar. The new ketones were employed in the dioxirane-mediated epoxidation of a range of trans- and trisubstituted arylalkenes giving enantiomeric excesses from low to good (30-90%). The effect of the size of the steric sensor on the enantioselectivity was also studied. The least bulky group (methoxy group) enhanced the stereoselectivity (up to 90% ee toward triphenylethylene). (C) 2011 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2011.07.014

文献信息

• Highly functionalized, enantiomerically pure furo[x,y-c]pyrans via alkylidenecarbenes derived from sugar templates: synthesis and mechanism study via computational chemistry
  作者：Albert Nguyen Van Nhien、Romaric Cordonnier、Marie-Delphine Le Bas、Sébastien Delacroix、Elena Soriano、José Marco-Contelles、Denis Postel

  DOI：10.1016/j.tet.2009.08.080

  日期：2009.11

  method for the generation of alkylidenecarbenes based on the reaction of trimethylsilylazide/Bu2SnO with α-cyanomesylates has been applied to readily available sugar derivatives for the synthesis of highly functionalized, enantiomerically pure furo[x,y-c]pyrans. The furo[x,y-c]pyran heterocyclic ring system is present in a number of natural or non-natural products of biological interest such as the miharamycins

  基于三甲基甲硅烷基叠氮化物/ Bu 2 SnO与α-氰基甲磺酸酯反应生成亚烷基卡宾的新方法已应用于容易获得的糖衍生物，用于合成高度官能化，对映体纯的呋喃[ x，y - c ]吡喃。呋喃[ x，y - c ]吡喃杂环系统存在于许多具有生物学意义的天然或非天然产物中，例如米拉霉素，应引起特别注意。本新方法的范围和程度已通过对起始糖前体（d-葡萄糖，d半乳糖等），在HEXO-α（β） - d -pyranoside形式，轴承也不同ø -保护基，该取代基的绝对构型的在异头位置的影响，位置（C-2， - 3和-4）在吡喃核上的亚烷基碳烯种类，以及在1,5 C–H键插入过程中“碳供体”处的取代（H或Ph）。总体而言，使用这些关键的1,5个C–H键插入反应，可合成呋喃[ x，y - c吡喃，很难用其他方法从中等到良好的产率制备。为了检查亚烷基卡宾的反应性，我们使用密度泛函理论对各种亚烷基卡宾衍生物插入C–H键的插入反应进行了系统的研究。
• Improved synthetic method for preparing spiro α-chloroepoxides
  作者：Ken-ichi Sato、Takao Sekiguchi、Tetsuya Hozumi、Toshiya Yamazaki、Shoji Akai

  DOI：10.1016/s0040-4039(02)00302-7

  日期：2002.4

  A new synthetic method via α-chloroolefine derivatives for preparing epimers of spiro α-chloroepoxides (2-chloro-oxyrane derivatives), which are useful key intermediates for the synthesis of branched-chain functionalized compounds, is developed as an alternative to previous methods requiring dichloromethyllithium.

  作为替代以前需要的方法的替代方法，开发了一种新的合成方法，该方法通过α-氯烯烃衍生物来制备螺α-氯环氧化合物（2-氯-氧杂环戊烷衍生物）的差向异构体，该化合物是合成支链官能化化合物的有用关键中间体。二氯甲基锂。
• Complementary stereoselectivity in the reactions of hexopyranosid-4-uloses with methylmagnesium iodide and methyllithium
  作者：Juji Yoshimura、Ken-Ichi Sato

  DOI：10.1016/0008-6215(83)88491-2

  日期：1983.11
• New mannose-derived ketones as organocatalysts for enantioselective dioxirane-mediated epoxidation of arylalkenes. Part 3: Chiral ketones from sugars
  作者：José M. Vega-Pérez、Ignacio Periñán、Margarita Vega-Holm、Carlos Palo-Nieto、Fernando Iglesias-Guerra

  DOI：10.1016/j.tet.2011.07.014

  日期：2011.9

  New D-arabino-hexopyranosid-3-uloses were synthesized by a simple method from mannopyranoside derivatives. The common skeleton possesses a tunable alkoxy group as steric sensor on carbon 2 of the sugar. The new ketones were employed in the dioxirane-mediated epoxidation of a range of trans- and trisubstituted arylalkenes giving enantiomeric excesses from low to good (30-90%). The effect of the size of the steric sensor on the enantioselectivity was also studied. The least bulky group (methoxy group) enhanced the stereoselectivity (up to 90% ee toward triphenylethylene). (C) 2011 Elsevier Ltd. All rights reserved.
• Novel methods for synthesizing 2-chloroaldehyde from carbonyl compounds and converting it into 2-hydroxyaldehyde derivatives
  作者：Ken-ichi Sato、Takao Sekiguchi、Shoji Akai

  DOI：10.1016/s0040-4039(01)00522-6

  日期：2001.5

  2-Chloroaldehyde derivatives were synthesized from carbonyl compounds with [chloromethyl (dimethyl)sulfonium trifluoromethanesulfonate, (1)] and DBU in THF in good yields. Further, 2-chloroaldehyde derivatives were converted into the corresponding 2-hydroxyaldehydes by treating the derivatives with n-Bu4NOH in good yields with the inverted configuration. The stereochemistry of all the products were

  由羰基化合物与[氯甲基（二甲基）ulf三氟甲烷磺酸盐（1）]和DBU在THF中以高收率合成了2-氯醛衍生物。此外，通过用n- Bu 4 NOH以高产率和反相构型处理衍生物，将2-氯醛衍生物转化为相应的2-羟基醛。所有产物的立体化学通过NMR（NOE）测定。