methyl 2,3''-anhydro-4,6-O-benzylidene-3-C-[(Z)-(hydroxymethyl)methylene]-α-D-ribo-hexopyranoside | 488820-54-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 呋喃吡喃类
• 英文名称: methyl 2,3''-anhydro-4,6-O-benzylidene-3-C-[(Z)-(hydroxymethyl)methylene]-α-D-ribo-hexopyranoside
• 英文别名: (2R,4aR,6S,6aR,9bS)-4,4a,6,6a,8,9b-hexahydro-6-methoxy-2-phenyl-furo[3',2':4,5]pyrano[3,2-d][1,3]dioxin；(1S,6R,7S,9R,12R)-7-methoxy-12-phenyl-5,8,11,13-tetraoxatricyclo[7.4.0.02,6]tridec-2-ene
• CAS: 488820-54-8
• 化学式: C₁₆H₁₈O₅
• 分子量: 290.316
• InChiKey: NJJSCUUPMYONEI-JKJDWNRSSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.5
• 重原子数：
  21
• 可旋转键数：
  2
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  46.2
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  methyl 2,3''-anhydro-4,6-O-benzylidene-3-C-[(Z)-(hydroxymethyl)methylene]-α-D-ribo-hexopyranoside 在 吡啶 、 四氧化锇 作用下， 反应 3.0h， 以80%的产率得到methyl 2,3"-anhydro-4,6-O-benzylidene-3-C-[(R)-1,2-dihydroxyethyl]-α-D-glucopyranoside
  参考文献：
  名称：

  SYNTHETIC APPROACH TO TETRAHYDROFURAN UNITS AND FIVE-MEMBERED RING LACTONES FUSED TO HEXOPYRANOSIDES ^*

  摘要：

  A stereoselective synthesis of the miharamycin sugar moiety epimer at C-3' was accomplished in high yield starting from an appropriate (Z)-Wittig product, synthesized by Wittig reaction of a 4,6-O-benzylidene protected hexopyranosid-3-ulose with [(ethoxycarbonyl)methylene]triphenylphosphorane followed by iodine promoted isomerisation of the (E)-Wittig product formed. Reduction of the (Z)-isomer obtained in quantitative yield, cyclisation and dihydroxylation with osmium tetroxide, gave the target molecule containing a cis-fused tetrahydrofuran ring in its structure. Synhesis of five-membered rings trans-fused to the hexopyranosidic units succeeded via two different synthetic pathways. Stereoselective Reformatsky reaction of a 2,6-di-O-pivaloyl protected hexopyranosid-3-ulose, followed by cyclisation with dimethylzinc gave a 3,4-trans-fused lactone. The approach using the reaction of 2,3-and 3,4-epoxides with the dianion of phenylselenoacetic acid led to low yield but novel phenylseleno derivatives of trans-fused five-membered rings, namely a phenylselenolactone 2,3-trans-fused to a 4,6-O-benzylidenehexopyranoside and a phenylselenolactenol 3,4-trans-fused to a 6-O-pivaloyl-hexopyranoside.

  DOI：

  10.1081/car-120013489
• 作为产物：
  描述：

  ethyl [(3Z)-(methyl 2-O-benzoyl-(R)-4,6-O-benzylidene-3-deoxy-α-D-ribohexopyranosid-3-ylidene)]acetate 在 lithium aluminium tetrahydride 、 4 A molecular sieve 、 三苯基膦 、 偶氮二甲酸二乙酯 作用下， 以 四氢呋喃 、 氯仿 为溶剂， 反应 9.5h， 生成 methyl 2,3''-anhydro-4,6-O-benzylidene-3-C-[(Z)-(hydroxymethyl)methylene]-α-D-ribo-hexopyranoside
  参考文献：
  名称：

  SYNTHETIC APPROACH TO TETRAHYDROFURAN UNITS AND FIVE-MEMBERED RING LACTONES FUSED TO HEXOPYRANOSIDES ^*

  摘要：

  A stereoselective synthesis of the miharamycin sugar moiety epimer at C-3' was accomplished in high yield starting from an appropriate (Z)-Wittig product, synthesized by Wittig reaction of a 4,6-O-benzylidene protected hexopyranosid-3-ulose with [(ethoxycarbonyl)methylene]triphenylphosphorane followed by iodine promoted isomerisation of the (E)-Wittig product formed. Reduction of the (Z)-isomer obtained in quantitative yield, cyclisation and dihydroxylation with osmium tetroxide, gave the target molecule containing a cis-fused tetrahydrofuran ring in its structure. Synhesis of five-membered rings trans-fused to the hexopyranosidic units succeeded via two different synthetic pathways. Stereoselective Reformatsky reaction of a 2,6-di-O-pivaloyl protected hexopyranosid-3-ulose, followed by cyclisation with dimethylzinc gave a 3,4-trans-fused lactone. The approach using the reaction of 2,3-and 3,4-epoxides with the dianion of phenylselenoacetic acid led to low yield but novel phenylseleno derivatives of trans-fused five-membered rings, namely a phenylselenolactone 2,3-trans-fused to a 4,6-O-benzylidenehexopyranoside and a phenylselenolactenol 3,4-trans-fused to a 6-O-pivaloyl-hexopyranoside.

  DOI：

  10.1081/car-120013489

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。
• SYNTHETIC APPROACH TO TETRAHYDROFURAN UNITS AND FIVE-MEMBERED RING LACTONES FUSED TO HEXOPYRANOSIDES ^*
  作者：Amélia P. Rauter、Olga Oliveira、Tana Canda、Estelle Leroi、Humberto Ferreira、Maria J. Ferreira、José A. Ascenso

  DOI：10.1081/car-120013489

  日期：2002.9.23

  A stereoselective synthesis of the miharamycin sugar moiety epimer at C-3' was accomplished in high yield starting from an appropriate (Z)-Wittig product, synthesized by Wittig reaction of a 4,6-O-benzylidene protected hexopyranosid-3-ulose with [(ethoxycarbonyl)methylene]triphenylphosphorane followed by iodine promoted isomerisation of the (E)-Wittig product formed. Reduction of the (Z)-isomer obtained in quantitative yield, cyclisation and dihydroxylation with osmium tetroxide, gave the target molecule containing a cis-fused tetrahydrofuran ring in its structure. Synhesis of five-membered rings trans-fused to the hexopyranosidic units succeeded via two different synthetic pathways. Stereoselective Reformatsky reaction of a 2,6-di-O-pivaloyl protected hexopyranosid-3-ulose, followed by cyclisation with dimethylzinc gave a 3,4-trans-fused lactone. The approach using the reaction of 2,3-and 3,4-epoxides with the dianion of phenylselenoacetic acid led to low yield but novel phenylseleno derivatives of trans-fused five-membered rings, namely a phenylselenolactone 2,3-trans-fused to a 4,6-O-benzylidenehexopyranoside and a phenylselenolactenol 3,4-trans-fused to a 6-O-pivaloyl-hexopyranoside.