Methanesulfonic acid (E)-(1R,2R,5S,6R)-5-hydroxy-1-((E)-(3S,4R)-3-hydroxy-4-methoxymethoxy-hept-5-enyl)-2-methanesulfonyloxy-6-methoxymethoxy-non-7-enyl ester | 177854-18-1

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机磺酸及其衍生物
• 英文名称: Methanesulfonic acid (E)-(1R,2R,5S,6R)-5-hydroxy-1-((E)-(3S,4R)-3-hydroxy-4-methoxymethoxy-hept-5-enyl)-2-methanesulfonyloxy-6-methoxymethoxy-non-7-enyl ester
• 英文别名: [(2E,4R,5S,8R,9R,12S,13R,14E)-5,12-dihydroxy-4,13-bis(methoxymethoxy)-9-methylsulfonyloxyhexadeca-2,14-dien-8-yl] methanesulfonate
• CAS: 177854-18-1
• 化学式: C₂₂H₄₂O₁₂S₂
• 分子量: 562.7
• InChiKey: UMGADJHVBOMQMY-IGOWMLTNSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.8
• 重原子数：
  36
• 可旋转键数：
  21
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.82
• 拓扑面积：
  181
• 氢给体数：
  2
• 氢受体数：
  12

反应信息

• 作为反应物：
  描述：

  Methanesulfonic acid (E)-(1R,2R,5S,6R)-5-hydroxy-1-((E)-(3S,4R)-3-hydroxy-4-methoxymethoxy-hept-5-enyl)-2-methanesulfonyloxy-6-methoxymethoxy-non-7-enyl ester 在 sodium hydride 作用下， 以 四氢呋喃 为溶剂， 以50%的产率得到(2S,5S,2'S,5'S)-5,5'-Bis-((E)-(R)-1-methoxymethoxy-but-2-enyl)-octahydro-[2,2']bifuranyl
  参考文献：
  名称：

  An Efficient Bidirectional Approach to the C₂-Symmetric Stereoisomers of the Bistetrahydrofuran Core of the Acetogenins

  摘要：

  A bidirectional route to nonracemic C-2-symmetric bistetrahydrofuran units related to acetogenin natural products was developed starting from the (S,S)-tartrate-derived dialdehyde 3.3. Bis-homologation with the (R)-alpha-OMOM crotylstannane (R)-4.1 in the presence of InCl3 afforded the anti adduct, diol 4.3. The derived tosylate 4.4, upon treatment with TBAF in THF, underwent sequential TBS cleavage and cyclization to the (R,R,R,R,R,R)-bis-OMOM bistetrahydrofuran 4.7. The epimeric (S,R,R,R,R,S)-bis-OMOM bistetrahydrofuran 4.10 was prepared along similar lines, except that the (R)-alpha-OMOM crotylstannane (R)-4.1 was first converted to the (R)-gamma-isomer (R)-4.2 with BF3 . OEt(2). Subsequent addition of dialdehyde 3.3 led to the diol adduct 4.5, which after tosylation and treatment with TBAF, yielded the bistetrahydrofuran 4.10. By repeating the aforementioned sequences, but starting with the (S)-alpha-OMOM-crotylstannane (S)-4.1, the (S,S-R,R,S,S)- and the (R,S,R,R,S,R)-bistetrahydrofurans 5.5 and 5.8 were prepared. A variation on the foregoing sequence in which the OTBS grouping of the adduct was converted to a mesylate and the OH group was used to effect intramolecular displacement was also examined. Accordingly, adduct ent-5.3 from BF3-promoted addition of stannane (R)-4.2 and ent-3.3, the enantiomer of aldehyde 3.3, was acetylated. Cleavage of the TBS ether followed by mesylate formation and then concommitant acetate hydrolysis and cyclization with methanolic Triton B yielded the bis-OMOM bistetrahydrofuran 5.5. An analogous sequence was used to convert adduct 4.3 to ent-4.10. In this case, acetate saponification was effected with methanolic K2CO3, and the resulting diol, 7.4, was cyclized with NaH in THF.

  DOI：

  10.1021/jo9603789
• 作为产物：
  描述：

  4(R),5(R)-bis(tert-butyldimethylsilyl)oxyoctadialdehyde 在 吡啶 、 4-二甲氨基吡啶 、 indium(III) chloride 、 四丁基氟化铵 、 水 、 potassium carbonate 、 三乙胺 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 乙酸乙酯 为溶剂， 反应 5.0h， 生成 Methanesulfonic acid (E)-(1R,2R,5S,6R)-5-hydroxy-1-((E)-(3S,4R)-3-hydroxy-4-methoxymethoxy-hept-5-enyl)-2-methanesulfonyloxy-6-methoxymethoxy-non-7-enyl ester
  参考文献：
  名称：

  An Efficient Bidirectional Approach to the C₂-Symmetric Stereoisomers of the Bistetrahydrofuran Core of the Acetogenins

  摘要：

  A bidirectional route to nonracemic C-2-symmetric bistetrahydrofuran units related to acetogenin natural products was developed starting from the (S,S)-tartrate-derived dialdehyde 3.3. Bis-homologation with the (R)-alpha-OMOM crotylstannane (R)-4.1 in the presence of InCl3 afforded the anti adduct, diol 4.3. The derived tosylate 4.4, upon treatment with TBAF in THF, underwent sequential TBS cleavage and cyclization to the (R,R,R,R,R,R)-bis-OMOM bistetrahydrofuran 4.7. The epimeric (S,R,R,R,R,S)-bis-OMOM bistetrahydrofuran 4.10 was prepared along similar lines, except that the (R)-alpha-OMOM crotylstannane (R)-4.1 was first converted to the (R)-gamma-isomer (R)-4.2 with BF3 . OEt(2). Subsequent addition of dialdehyde 3.3 led to the diol adduct 4.5, which after tosylation and treatment with TBAF, yielded the bistetrahydrofuran 4.10. By repeating the aforementioned sequences, but starting with the (S)-alpha-OMOM-crotylstannane (S)-4.1, the (S,S-R,R,S,S)- and the (R,S,R,R,S,R)-bistetrahydrofurans 5.5 and 5.8 were prepared. A variation on the foregoing sequence in which the OTBS grouping of the adduct was converted to a mesylate and the OH group was used to effect intramolecular displacement was also examined. Accordingly, adduct ent-5.3 from BF3-promoted addition of stannane (R)-4.2 and ent-3.3, the enantiomer of aldehyde 3.3, was acetylated. Cleavage of the TBS ether followed by mesylate formation and then concommitant acetate hydrolysis and cyclization with methanolic Triton B yielded the bis-OMOM bistetrahydrofuran 5.5. An analogous sequence was used to convert adduct 4.3 to ent-4.10. In this case, acetate saponification was effected with methanolic K2CO3, and the resulting diol, 7.4, was cyclized with NaH in THF.

  DOI：

  10.1021/jo9603789

文献信息

• An Efficient Bidirectional Approach to the <i>C</i>₂-Symmetric Stereoisomers of the Bistetrahydrofuran Core of the Acetogenins
  作者：James A. Marshall、Kevin W. Hinkle

  DOI：10.1021/jo9603789

  日期：1996.1.1

  A bidirectional route to nonracemic C-2-symmetric bistetrahydrofuran units related to acetogenin natural products was developed starting from the (S,S)-tartrate-derived dialdehyde 3.3. Bis-homologation with the (R)-alpha-OMOM crotylstannane (R)-4.1 in the presence of InCl3 afforded the anti adduct, diol 4.3. The derived tosylate 4.4, upon treatment with TBAF in THF, underwent sequential TBS cleavage and cyclization to the (R,R,R,R,R,R)-bis-OMOM bistetrahydrofuran 4.7. The epimeric (S,R,R,R,R,S)-bis-OMOM bistetrahydrofuran 4.10 was prepared along similar lines, except that the (R)-alpha-OMOM crotylstannane (R)-4.1 was first converted to the (R)-gamma-isomer (R)-4.2 with BF3 . OEt(2). Subsequent addition of dialdehyde 3.3 led to the diol adduct 4.5, which after tosylation and treatment with TBAF, yielded the bistetrahydrofuran 4.10. By repeating the aforementioned sequences, but starting with the (S)-alpha-OMOM-crotylstannane (S)-4.1, the (S,S-R,R,S,S)- and the (R,S,R,R,S,R)-bistetrahydrofurans 5.5 and 5.8 were prepared. A variation on the foregoing sequence in which the OTBS grouping of the adduct was converted to a mesylate and the OH group was used to effect intramolecular displacement was also examined. Accordingly, adduct ent-5.3 from BF3-promoted addition of stannane (R)-4.2 and ent-3.3, the enantiomer of aldehyde 3.3, was acetylated. Cleavage of the TBS ether followed by mesylate formation and then concommitant acetate hydrolysis and cyclization with methanolic Triton B yielded the bis-OMOM bistetrahydrofuran 5.5. An analogous sequence was used to convert adduct 4.3 to ent-4.10. In this case, acetate saponification was effected with methanolic K2CO3, and the resulting diol, 7.4, was cyclized with NaH in THF.