(2E,6E)-(4R,5R)-4,5-Bis-(tert-butyl-dimethyl-silanyloxy)-octa-2,6-dienedioic acid diethyl ester | 141247-15-6

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: (2E,6E)-(4R,5R)-4,5-Bis-(tert-butyl-dimethyl-silanyloxy)-octa-2,6-dienedioic acid diethyl ester
• 英文别名: diethyl (2E,4R,5R,6E)-4,5-bis[[tert-butyl(dimethyl)silyl]oxy]octa-2,6-dienedioate
• CAS: 141247-15-6
• 化学式: C₂₄H₄₆O₆Si₂
• 分子量: 486.797
• InChiKey: GDMVSENXIZFNJM-AZBDOTAUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.01
• 重原子数：
  32
• 可旋转键数：
  15
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  71.1
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  (2E,6E)-(4R,5R)-4,5-Bis-(tert-butyl-dimethyl-silanyloxy)-octa-2,6-dienedioic acid diethyl ester 在 palladium on activated charcoal indium(III) chloride 、 氢气 、 二异丁基氢化铝 作用下， 以 乙酸乙酯 、 甲苯 为溶剂， -78.0 ℃ 、101.33 kPa 条件下， 反应 17.0h， 生成 (2E,14E)-(4R,5S,8R,9R,12S,13R)-8,9-Bis-(tert-butyl-dimethyl-silanyloxy)-4,13-bis-methoxymethoxy-hexadeca-2,14-diene-5,12-diol
  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：

  (4R,5R)-{5-[(E)-2''-ethoxycarbonyl-vinyl]-2',2'-dimethyl-[1',3']-dioxolan-4-yl}-(E)-acrylic acid ethyl ester 在 咪唑 、 三氟化硼乙醚 、 1,2-乙二硫醇 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 24.17h， 生成 (2E,6E)-(4R,5R)-4,5-Bis-(tert-butyl-dimethyl-silanyloxy)-octa-2,6-dienedioic acid diethyl ester
  参考文献：
  名称：

  光学活性烯丙基烯醇醇的非对映选择性二羟基化衍生的多羟基化合物的化学选择性

  摘要：

  描述了一种用于制备几种多元醇及其相应的乳糖醇和内酯的有效，实用和立体选择性的途径。它们是合成几种结构有趣的化合物的有前途的前体。

  DOI：

  10.1016/0040-4020(96)00357-2

文献信息

• Stereoselective synthesis of optically active mono and diaminoalcohols
  作者：M. Teresa Barros、M. Adilia Januário Charmier、Christopher D. Maycock、Thierry Michaud

  DOI：10.1016/j.tet.2005.06.011

  日期：2005.8

  Several optically active mono and diaminopolyols have been synthesized starting from the octadienedioate 1, by regio- and stereo selective azidation of the corresponding alcohol by Mitsunobu/SN2 substitution.

  几个光学活性单和diaminopolyols已经合成从octadienedioate开始1，由相应的醇的区域选择性和立体选择性的叠氮化通过光延/ S Ñ 2取代。
• Synthesis of γ-lactones by desymmetrization. A synthesis of (−)-muricatacin
  作者：M. Teresa Barros、M. Adilia Januario Charmier、Christopher D. Maycock、Thierry Michaud

  DOI：10.1016/j.tet.2008.10.020

  日期：2009.1

  A short synthesis of the natural potent cytotoxic agent (-)-muricatacin 1 and related unsaturated lactones from a versatile common intermediate, dienedioate 2, derived from D-mannitol or tartaric acid, is described. The strategy depends upon the desymmetrization of 7 by dihydroxylation and elaboration of the hydroxy alkyl sidechain. A route to unsaturated lactones is also described using a cis selective Wittig reaction. Since the enantiomers of 2 are available from the corresponding tartaric acids, this method provides access to both enantiomers of the described compounds and a wide range of derivatives. (C) 2008 Elsevier Ltd. All rights reserved.