methyl {(2S,3S,6R)-{[1E,3E,7E,11R,10R,9S,5S]-11-tert-butyldimethylsiloxy-10-methoxy-1,5,7,9-tetramethyldodeca-1,3,7-trienyl}-3-methyloxan-6-yl}ethanoate | 329366-77-0

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: methyl {(2S,3S,6R)-{[1E,3E,7E,11R,10R,9S,5S]-11-tert-butyldimethylsiloxy-10-methoxy-1,5,7,9-tetramethyldodeca-1,3,7-trienyl}-3-methyloxan-6-yl}ethanoate
• 英文别名: methyl 2-{(2R,5S,6S)-6-[(2E,4E,6S,8E,10S,11R,12R)-12-(tert-Butyldimethylsilyloxy)-11-methoxy-6,8,10-trimethyltrideca-2,4,8-trien-2-yl]-5-methyltetrahydro-2H-pyran-2-yl}acetate；methyl 2-[(2R,5S,6S)-6-[(2E,4E,6S,8E,10S,11R,12R)-12-[tert-butyl(dimethyl)silyl]oxy-11-methoxy-6,8,10-trimethyltrideca-2,4,8-trien-2-yl]-5-methyloxan-2-yl]acetate
• CAS: 329366-77-0
• 化学式: C₃₂H₅₈O₅Si
• 分子量: 550.895
• InChiKey: ABLAIXFDTTWTHS-DPDZTHGVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.27
• 重原子数：
  38
• 可旋转键数：
  15
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.78
• 拓扑面积：
  54
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  methyl {(2S,3S,6R)-{[1E,3E,7E,11R,10R,9S,5S]-11-tert-butyldimethylsiloxy-10-methoxy-1,5,7,9-tetramethyldodeca-1,3,7-trienyl}-3-methyloxan-6-yl}ethanoate 在 盐酸 、 叔丁基过氧化氢 、 bis(acetylacetonate)oxovanadium 、 三甲基氢氧化锡 作用下， 以 甲醇 、 1,1-二氯乙烷 、 苯 为溶剂， 反应 6.0h， 生成 3-{[(6,7-二乙氧基-1,2,3,4-四氢萘-2-基)氨基]甲基}-6-(乙烯氧基)环己-2,4-二烯-1-酮盐酸
  参考文献：
  名称：

  A Stereoselective Synthesis of (+)-Herboxidiene/GEX1A

  摘要：

  A stereoselective synthesis of (+)-herboxidiene is described. The convergent synthesis utilized a Suzuki cross-coupling reaction to assemble the key segments. The synthesis of the functionalized tetrahydropyran ring utilized an Achmatowicz reaction as the key step. The synthesis of the C10-C19 segment was accomplished using Brown's crotylboration, asymmetric alkylation, and a stereoselective allylic chlorination reactions.

  DOI：

  10.1021/ol102549a
• 作为产物：
  描述：

  (2S,6S)-2-allyl-6-((tert-butyldimethylsilyloxy)methyl)-2H-pyran-3(6H)-one 在 chromium dichloride 、 盐酸 、 4-二甲氨基吡啶 、 platinum(IV) oxide 、 sodium chlorite 、 sodium tetrahydroborate 、 四(三苯基膦)钯 、 2,6-二叔丁基吡啶 、 sodium dihydrogenphosphate dihydrate 、 二甲基硫 、 偶氮二异丁腈 、 cerium(III) chloride heptahydrate 、 三(三甲基硅基)硅烷 、 硫酸 、 氢气 、 diethylzinc 、 potassium carbonate 、 caesium carbonate 、 戴斯-马丁氧化剂 、 臭氧 、 mercury(II) sulfate 、 盐酸-N-乙基-Nˊ-(3-二甲氨基丙基)碳二亚胺 作用下， 以 四氢呋喃 、 甲醇 、 2-甲基-2-丁烯 、 正己烷 、 二氯甲烷 、 水 、 甲苯 、 叔丁醇 为溶剂， 反应 24.92h， 生成 methyl {(2S,3S,6R)-{[1E,3E,7E,11R,10R,9S,5S]-11-tert-butyldimethylsiloxy-10-methoxy-1,5,7,9-tetramethyldodeca-1,3,7-trienyl}-3-methyloxan-6-yl}ethanoate
  参考文献：
  名称：

  A Stereoselective Synthesis of (+)-Herboxidiene/GEX1A

  摘要：

  A stereoselective synthesis of (+)-herboxidiene is described. The convergent synthesis utilized a Suzuki cross-coupling reaction to assemble the key segments. The synthesis of the functionalized tetrahydropyran ring utilized an Achmatowicz reaction as the key step. The synthesis of the C10-C19 segment was accomplished using Brown's crotylboration, asymmetric alkylation, and a stereoselective allylic chlorination reactions.

  DOI：

  10.1021/ol102549a

文献信息

• A Formal Synthesis of Herboxidiene/GEX1A
  作者：Jhillu S. Yadav、G. Madhusudhan Reddy、S. Rehana Anjum、B. V. Subba Reddy

  DOI：10.1002/ejoc.201402235

  日期：2014.7

  A formal synthesis of herboxidiene/GEX 1A is described. This approach demonstrates successful application of the Prins cyclization for the construction of the tetrahydropyran core of the target molecule. The chirality of the side chain has been established through the Sharpless asymmetric dihydroxylation and Evan's alkylation. The olefin cross-metathesis was applied to couple both key fragments.

  描述了herboxidiene/GEX 1A 的正式合成。这种方法证明了 Prins 环化在构建目标分子的四氢吡喃核心中的成功应用。侧链的手性是通过 Sharpless 不对称二羟基化和 Evan 烷基化建立的。应用烯烃交叉复分解来偶联两个关键片段。
• A Total Synthesis of Herboxidiene Methyl Ester
  作者：Martin G. Banwell、Rajaratnam Premraj、Malcolm D. McLeod、Gregory W. Simpson

  DOI：10.3987/com-12-12597

  日期：——

  The total synthesis of the methyl ester, 35, of herboxidiene (1, a.k.a. GEX1A and TAN-1609), a polyketide displaying both herbicidal and anti-tumor activity, is described. The convergent reaction sequence involves, in its closing stages, the union of the phosphine oxide 3 with the aldehyde 21 to deliver, via a Horner-Wittig reaction with accompanying epimerization at C12, compound 33 that after deprotection affords an alcohol, 34, capable of participating in a regio- and diastereo-selective epoxidation reaction to give target 35. Phosphine oxide 3 was prepared via the intramolecular hetero-Michael addition of a secondary alcohol to a tethered and Z-configured acrylate while aldehyde 21 was generated, in the crucial step of the relevant reaction sequence, via an Ireland-Claisen rearrangement reaction.
• A Stereoselective Synthesis of (+)-Herboxidiene/GEX1A
  作者：Arun K. Ghosh、Jianfeng Li

  DOI：10.1021/ol102549a

  日期：2011.1.7

  A stereoselective synthesis of (+)-herboxidiene is described. The convergent synthesis utilized a Suzuki cross-coupling reaction to assemble the key segments. The synthesis of the functionalized tetrahydropyran ring utilized an Achmatowicz reaction as the key step. The synthesis of the C10-C19 segment was accomplished using Brown's crotylboration, asymmetric alkylation, and a stereoselective allylic chlorination reactions.