methyl (S)-5-hydroxy-2-[(2R,3R)-3-methyl-5-oxotetrahydrofuran-2-yl]-4-oxochroman2-carboxylate | 1571891-65-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并吡喃
• 英文名称: methyl (S)-5-hydroxy-2-[(2R,3R)-3-methyl-5-oxotetrahydrofuran-2-yl]-4-oxochroman2-carboxylate
• 英文别名: methyl (S)-5-hydroxy-2-([2R,3R]-3-methyl-5-oxotetrahydrofuran-2-yl)-4-oxochromane-2-carboxylate；methyl (2S)-5-hydroxy-2-[(2R,3R)-3-methyl-5-oxooxolan-2-yl]-4-oxo-3H-chromene-2-carboxylate
• CAS: 1571891-65-0
• 化学式: C₁₆H₁₆O₇
• 分子量: 320.299
• InChiKey: QOBIDOOHIOXPIA-VXSYNFHWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  23
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.44
• 拓扑面积：
  99.1
• 氢给体数：
  1
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  methyl (S)-5-hydroxy-2-[(2R,3R)-3-methyl-5-oxotetrahydrofuran-2-yl]-4-oxochroman2-carboxylate 在 C₁₀H₁₆N⁽¹⁺⁾*Cl^(1-)*ICl 、 calcium carbonate 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 3.0h， 以50%的产率得到methyl (S)-5-hydroxy-6-iodo-2-([2R,3R]-3-methyl-5-oxotetrahydrofuran-2-yl)-4-oxochromane-2-carboxylate
  参考文献：
  名称：

  布雷诺利德H和Phomopsis-H76 A的对映选择性全合成及其结构测定

  摘要：

  这项工作报告了两个二聚体天然苯并二氢吡喃酮内酯phomopsis-H76 A（5）和blennolide H（6）的对映选择性全合成。两种合成都可以通过色氨酸11来实现，而色氨酸11是通过对映选择性Wacker型环化反应，ee大于99％获得的。相应的单体的二聚是使用钯催化的Suzuki反应进行的。此外，在这项工作中，可以修改phomopsis-H76 A的绝对构型，并确定布列诺利德H的相对构型和绝对构型。

  DOI：

  10.1002/chem.201801323
• 作为产物：
  描述：

  methyl (S)-5-methoxy-2-[(2R,3R)-3-methyl-5-oxotetrahydrofuran-2-yl]chroman-2carboxylate 在 叔丁基过氧化氢 、 dirhodium tetrakis(caprolactamate) 、 三溴化硼 、 碳酸氢钠 作用下， 以 癸烷 、 二氯甲烷 、 1,2-二氯乙烷 为溶剂， 反应 26.0h， 生成 methyl (S)-5-hydroxy-2-[(2R,3R)-3-methyl-5-oxotetrahydrofuran-2-yl]-4-oxochroman2-carboxylate
  参考文献：
  名称：

  The Paecilin Puzzle ‒ Enantioselective Synthesis of the Proposed Structures of Paecilin A and B

  摘要：

  For the synthesis of the two diastereomers 3c and 3d of the proposed structure of paecilin B (3) phenol 19, containing an alkenyl moiety, was treated with Pd(II) in the presence of the chiral BOXAX ligand 9b to give 20 with 96% ee. A subsequent Sharpless dihydroxylation afforded two isomeric diols, which were further transfoimed into 31 and 32. The final steps included removal of the silyl protecting group with simultaneous lactone formation, oxidation and cleavage of the methyl ether. For the preparation of the dimeric paecilin A (1) brominated intermediate 38 was treated with (Bpin)(2), S-Phos and Pd(OAc)(2). The spectroscopic data of the new compounds did not match those of the isolated natural products.

  DOI：

  10.3987/com-13-s(s)68

文献信息

• The Paecilin Puzzle ‒ Enantioselective Synthesis of the Proposed Structures of Paecilin A and B
  作者：Lutz F. Tietze、Ling Ma、Stefan Jackenkroll、Johannes R. Reiner、Judith Hierold、Boopathy Gnanaprakasam、Sven Heidemann

  DOI：10.3987/com-13-s(s)68

  日期：——

  For the synthesis of the two diastereomers 3c and 3d of the proposed structure of paecilin B (3) phenol 19, containing an alkenyl moiety, was treated with Pd(II) in the presence of the chiral BOXAX ligand 9b to give 20 with 96% ee. A subsequent Sharpless dihydroxylation afforded two isomeric diols, which were further transfoimed into 31 and 32. The final steps included removal of the silyl protecting group with simultaneous lactone formation, oxidation and cleavage of the methyl ether. For the preparation of the dimeric paecilin A (1) brominated intermediate 38 was treated with (Bpin)(2), S-Phos and Pd(OAc)(2). The spectroscopic data of the new compounds did not match those of the isolated natural products.
• Enantioselective Total Synthesis of Blennolide H and Phomopsis-H76 A and Determination of Their Structure
  作者：Guillermo Valdomir、Soundararasu Senthilkumar、Dhandapany Ganapathy、Yun Zhang、Lutz F. Tietze

  DOI：10.1002/chem.201801323

  日期：2018.6.21

  total synthesis of the two dimeric natural chromanone lactones phomopsis‐H76 A (5) and blennolide H (6). Both syntheses could be achieved from chromane 11, which was obtained by an enantioselective Wacker‐type cyclization with >99 % ee. The dimerization of the corresponding monomers was performed using a palladium‐catalyzed Suzuki reaction. Moreover, within this work it was possible to revise the absolute

  这项工作报告了两个二聚体天然苯并二氢吡喃酮内酯phomopsis-H76 A（5）和blennolide H（6）的对映选择性全合成。两种合成都可以通过色氨酸11来实现，而色氨酸11是通过对映选择性Wacker型环化反应，ee大于99％获得的。相应的单体的二聚是使用钯催化的Suzuki反应进行的。此外，在这项工作中，可以修改phomopsis-H76 A的绝对构型，并确定布列诺利德H的相对构型和绝对构型。