ethyl [(3Z)-(methyl 2-O-benzoyl-(R)-4,6-O-benzylidene-3-deoxy-α-D-ribohexopyranosid-3-ylidene)]acetate | 268746-27-6

• 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: ethyl [(3Z)-(methyl 2-O-benzoyl-(R)-4,6-O-benzylidene-3-deoxy-α-D-ribohexopyranosid-3-ylidene)]acetate
• 英文别名: methyl 2-O-benzoyl-4,6-O-benzylidene-3-C-[(Z)-(ethoxycarbonyl)methylene]-α-D-ribo-hexopyranoside；[(2R,4aR,6S,7R,8Z,8aS)-8-(2-ethoxy-2-oxoethylidene)-6-methoxy-2-phenyl-4a,6,7,8a-tetrahydro-4H-pyrano[3,2-d][1,3]dioxin-7-yl] benzoate
• CAS: 268746-27-6
• 化学式: C₂₅H₂₆O₈
• 分子量: 454.477
• InChiKey: CPWJLDYXIATBBN-BADXHVHTSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  33
• 可旋转键数：
  8
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  89.5
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为反应物：
  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 作用下， 以 四氢呋喃 为溶剂， 反应 3.0h， 以90%的产率得到methyl 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
• 作为产物：
  描述：

  methyl 2-O-benzoyl-4,6-di-O-benzylidene-α-D-glucopyranoside 在 重铬酸吡啶 、 乙酸酐 作用下， 以 二氯甲烷 、 氯仿 为溶剂， 反应 0.17h， 生成 ethyl [(3E)-(methyl 2-O-benzoyl-(R)-4,6-O-benzylidene-3-deoxy-α-D-ribohexopyranosid-3-ylidene)]acetate 、 ethyl [(3Z)-(methyl 2-O-benzoyl-(R)-4,6-O-benzylidene-3-deoxy-α-D-ribohexopyranosid-3-ylidene)]acetate
  参考文献：
  名称：

  Wittig Reaction: Domino Olefination and Stereoselectivity DFT Study. Synthesis of the Miharamycins’ Bicyclic Sugar Moiety

  摘要：

  2-O-Acyl protected-d-ribo-3-uloses reacted with [(ethoxycarbonyl)methylene]triphenylphosphorane in acetonitrile to afford regio- and stereoselectively 2-(Z)-alkenes in 10-60 min under microwave irradiation. This domino reaction is proposed to proceed via tautomerization of 3-ulose to enol, acyl migration, tautomerization to the 3-O-acyl-2-ulose, and Wittig reaction. Alternatively, in chloroform, regioselective 3-olefination of 2-O-pivaloyl-3-uloses gave (E)-alkenes, key precursors for the miharamycins' bicyclic sugar moiety.

  DOI：

  10.1021/acs.orglett.5b02849

文献信息

• Wittig Reaction: Domino Olefination and Stereoselectivity DFT Study. Synthesis of the Miharamycins’ Bicyclic Sugar Moiety
  作者：Vasco Cachatra、Andreia Almeida、João Sardinha、Susana D. Lucas、Ana Gomes、Pedro D. Vaz、M. Helena Florêncio、Rafael Nunes、Diogo Vila-Viçosa、Maria José Calhorda、Amélia P. Rauter

  DOI：10.1021/acs.orglett.5b02849

  日期：2015.11.20

  2-O-Acyl protected-d-ribo-3-uloses reacted with [(ethoxycarbonyl)methylene]triphenylphosphorane in acetonitrile to afford regio- and stereoselectively 2-(Z)-alkenes in 10-60 min under microwave irradiation. This domino reaction is proposed to proceed via tautomerization of 3-ulose to enol, acyl migration, tautomerization to the 3-O-acyl-2-ulose, and Wittig reaction. Alternatively, in chloroform, regioselective 3-olefination of 2-O-pivaloyl-3-uloses gave (E)-alkenes, key precursors for the miharamycins' bicyclic sugar moiety.
• 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.