methyl 4,6-O-benzylidene-2(S)-deoxy-2-C-[2'(S)-(carboxy)phenylselenylmethyl]-α-D-ribo-hexopyranoside-3,2'-lactone

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二恶烷
• 英文名称: methyl 4,6-O-benzylidene-2(S)-deoxy-2-C-[2'(S)-(carboxy)phenylselenylmethyl]-α-D-ribo-hexopyranoside-3,2'-lactone
• 英文别名: (1S,2S,5S,6S,7S,9R,12R)-7-methoxy-12-phenyl-5-phenylselanyl-3,8,11,13-tetraoxatricyclo[7.4.0.02,6]tridecan-4-one
• 化学式: C₂₂H₂₂O₆Se
• 分子量: 461.373
• InChiKey: QJFPLQMZHYZDSN-XACANUDXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.83
• 重原子数：
  29
• 可旋转键数：
  4
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.41
• 拓扑面积：
  63.2
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为产物：
  描述：

  methyl 4,6-O-benzylidene-2,3-di-O-methanesulfonyl-α-D-glucopyranoside 在 sodium methylate 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 甲醇 、 正己烷 、 二氯甲烷 为溶剂， 反应 40.0h， 生成 methyl 4,6-O-benzylidene-2(S)-deoxy-2-C-[2'(S)-(carboxy)phenylselenylmethyl]-α-D-ribo-hexopyranoside-3,2'-lactone
  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

• 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.