(E)-(4S,5S)-Ethyl 6-<(tert-butyldimethylsilyl)oxy>-4,5-O-(1-methylethylidene)-2-hexenoate | 108817-98-7

• 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: (E)-(4S,5S)-Ethyl 6-<(tert-butyldimethylsilyl)oxy>-4,5-O-(1-methylethylidene)-2-hexenoate
• 英文别名: ethyl (E)-(4S,5S)-6-(tert-butyldimethylsilyloxy)-4,5-(1-methylethylidenedioxy)-2-hexenoate；Ethyl (2E,4S,5S)-6-tert-butyldimethylsilyloxy-4,5-isopropylidenedioxyhex-2-enoate；ethyl (E)-3-[(4S,5S)-5-[[tert-butyl(dimethyl)silyl]oxymethyl]-2,2-dimethyl-1,3-dioxolan-4-yl]prop-2-enoate
• CAS: 108817-98-7
• 化学式: C₁₇H₃₂O₅Si
• 分子量: 344.524
• InChiKey: BHRQSIQCBAFKOZ-NKVPIJFCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.65
• 重原子数：
  23
• 可旋转键数：
  8
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.82
• 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：

  (E)-(4S,5S)-Ethyl 6-<(tert-butyldimethylsilyl)oxy>-4,5-O-(1-methylethylidene)-2-hexenoate 在 palladium on activated charcoal 氢气 、 戴斯-马丁氧化剂 作用下， 以 乙醇 、 二氯甲烷 为溶剂， 反应 17.0h， 生成 ethyl (4S,5R)-5-formyl-4,5-isopropylidenedioxypentanoate
  参考文献：
  名称：

  Structure elucidation and synthesis of (4S,5S,6Z,8E )-5-hydroxydeca-6,8-dien-4-olide [(S,S)-sapinofuranone B]—a novel γ-lactone metabolite of Acremonium strictum

  摘要：

  (4S,5S,6Z,8E)-5-Hydroxydeca-6,8-dien-4-olide 是 Acremium strictum 的一种新型代谢物，其结构已通过光谱研究和与已知 L 因子的化学相关性确定。该结构已通过全合成得到证实，其中C-4和C-5处的不对称中心由L-酒石酸二甲酯精心设计，并通过(E)-prop-1的Stille偶联引入6,8-二烯部分-烯基三丁基锡与(Z)-乙烯基碘化物。最近分离的 Sphaeropsis sapinae 代谢物 Sapinofuranones A 和 B 的绝对构型显示为 A. strictum 代谢物的相应 (4R,5S) 和 (4R,5R) 非对映异构体。

  DOI：

  10.1039/b001823f
• 作为产物：
  描述：

  (-)-二甲基-2,3-邻异丙亚基-L-酒石酸酯 在 lithium aluminium tetrahydride 、 sodium hydride 作用下， 以 四氢呋喃 为溶剂， 生成 (E)-(4S,5S)-Ethyl 6-<(tert-butyldimethylsilyl)oxy>-4,5-O-(1-methylethylidene)-2-hexenoate
  参考文献：
  名称：

  Stereoselective synthesis of long-chain polyols by sequential homologation of enals with nonracemic .gamma.-silyloxy allylic stannanes and directed hydroxylation

  摘要：

  The nonracemic gamma-silyloxy allylic stannanes (S)-8 and (R)-8 add to the (R,R)-tartrate derived enals 7 and 24 to afford the adducts 9, 14, and 25. The bis-TBS derivatives 10, 15 and 22, upon hydroxylation with catalytic 0804-NMO, yield the differentially protected polyols 11, 16, and 23.

  DOI：

  10.1021/jo00074a004

文献信息

• Diazo Reagents in Copper(I)-Catalyzed Olefination of Aldehydes
  作者：Hélène Lebel、Michaël Davi

  DOI：10.1002/adsc.200800381

  日期：2008.10.6

  The olefination of aldehydes to synthesize unsaturated ketones, esters, amides and phosphonates using diazo reagents and triphenylphosphine in the presence of copper(I) iodide as catalyst, is described. Good to excellent E:Z selectivities as well as yields were obtained for a large variety of aliphatic, aromatic and heteroaromatic aldehydes. The reaction showed also an excellent functional group compatibility

  描述了在碘化铜（I）存在下使用重氮试剂和三苯基膦将醛烯化以合成不饱和酮，酯，酰胺和膦酸酯。对于多种脂族，芳族和杂芳族醛，均获得了良好的E：Z选择性和良好的收率。该反应还显示出优异的官能团相容性，并且在酮，硝基，胺，醚，缩醛，硫醚和卤化物基团的存在下醛被选择性地反应。与先前报道的昂贵的过渡金属络合物相比，使用成本有效的铜盐作为催化剂是有利的。该方法用于scutifoliamide A的全合成，scutifoliamide A是一种具有抗真菌活性的生物活性化合物。
• A convenient formal synthesis of (2S,3S)-3-hydroxy pipecolic acid
  作者：Subhash P. Chavan、Kishor R. Harale、Nilesh B. Dumare、Uttam R. Kalkote

  DOI：10.1016/j.tetasy.2011.02.023

  日期：2011.3

  A convenient synthesis of (2S,3S)-3-hydroxy pipecolic acid starting from inexpensive and easily available L-(+)-tartaric acid has been described. (C) 2011 Elsevier Ltd. All rights reserved.
• Stereoselective synthesis of long-chain polyols by sequential homologation of enals with nonracemic .gamma.-silyloxy allylic stannanes and directed hydroxylation
  作者：James A. Marshall、Serge Beaudoin、Krzysztof Lewinski

  DOI：10.1021/jo00074a004

  日期：1993.10

  The nonracemic gamma-silyloxy allylic stannanes (S)-8 and (R)-8 add to the (R,R)-tartrate derived enals 7 and 24 to afford the adducts 9, 14, and 25. The bis-TBS derivatives 10, 15 and 22, upon hydroxylation with catalytic 0804-NMO, yield the differentially protected polyols 11, 16, and 23.
• Stereoselective Synthesis of Higher Sugars by Homologation of Carbohydrate-Derived Enals with Nonracemic .gamma.-(Silyloxy) Allylic Stannanes and Substrate-Directed Hydroxylation
  作者：James A. Marshall、Serge Beaudoin

  DOI：10.1021/jo00101a020

  日期：1994.11

  A strategy is described for the chain extension of carbohydrate derivatives utilizing sequential Horner-Emmons condensation and then reduction-oxidation to prepare the enal homologue VII, which is converted to the corresponding dienyl bis-OTBS derivative IX upon condensation with a gamma-(silyloxy) allylic stannane VI and subsequent silylation. Dihydroxylation of dienes M with OsO4-NMO leads to syn,anti,syn,anti,syn. hexol derivatives X with excellent diastereoselectivity. These hexols undergo selective oxidative cleavage with H5IO6 to yield gamma-lactols XI. The methodology has been used to prepare the octonic lactone 15 from (S,S)-dimethyl tartrate and the undeconic lactone 32 from D-mannitol.
• Structure elucidation and synthesis of (4S,5S,6Z,8E )-5-hydroxydeca-6,8-dien-4-olide [(S,S)-sapinofuranone B]—a novel γ-lactone metabolite of Acremonium strictum
  作者：Sarah Clough、Mairi E. Raggatt、Thomas J. Simpson、Christine L. Willis、Andrew Whiting、Stephen K. Wrigley

  DOI：10.1039/b001823f

  日期：——

  The structure of (4S,5S,6Z,8E)-5-hydroxydeca-6,8-dien-4-olide, a novel metabolite of Acremonium strictum, has been established by spectroscopic studies and chemical correlation with the known L-factor. The structure has been confirmed by a total synthesis in which the asymmetric centres at C-4 and C-5 were elaborated from dimethyl L-tartrate and the 6,8-diene moiety was introduced via Stille coupling of (E)-prop-1-enyltributyltin with a (Z)-vinylic iodide. The absolute configurations of sapinofuranones A and B, recently isolated metabolites of Sphaeropsis sapinae, are shown to be the corresponding (4R,5S) and (4R,5R) diastereomers of the A. strictum metabolite.

  (4S,5S,6Z,8E)-5-Hydroxydeca-6,8-dien-4-olide 是 Acremium strictum 的一种新型代谢物，其结构已通过光谱研究和与已知 L 因子的化学相关性确定。该结构已通过全合成得到证实，其中C-4和C-5处的不对称中心由L-酒石酸二甲酯精心设计，并通过(E)-prop-1的Stille偶联引入6,8-二烯部分-烯基三丁基锡与(Z)-乙烯基碘化物。最近分离的 Sphaeropsis sapinae 代谢物 Sapinofuranones A 和 B 的绝对构型显示为 A. strictum 代谢物的相应 (4R,5S) 和 (4R,5R) 非对映异构体。