ethyl (2Z,4S)-4-<(tert-butyldimethylsilyl)oxy>-2-pentenoate | 113034-39-2

• 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: ethyl (2Z,4S)-4-<(tert-butyldimethylsilyl)oxy>-2-pentenoate
• 英文别名: (S)-ethyl-4-t-butyldimethylsilyloxy-2-(Z)-pentenoate；(S,Z)-ethyl 4-((tert-butyldimethylsilyl)oxy)pent-2-enoate；ethyl (S,Z)-4-(tert-butyldimethylsilyloxy)pent-2-enoate；ethyl (Z,4S)-4-[tert-butyl(dimethyl)silyl]oxypent-2-enoate
• CAS: 113034-39-2
• 化学式: C₁₃H₂₆O₃Si
• 分子量: 258.433
• InChiKey: JIPMHCMBHMJNGC-JUDLJHIGSA-N

物化性质

• 沸点：
  285.5±23.0 °C(Predicted)
• 密度：
  0.914±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.52
• 重原子数：
  17.0
• 可旋转键数：
  5.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.77
• 拓扑面积：
  35.53
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  ethyl (2Z,4S)-4-<(tert-butyldimethylsilyl)oxy>-2-pentenoate 在 水 、 lithium hydroxide 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 反应 6.0h， 以96.7%的产率得到(S,Z)-4-((tert-butyldimethylsilyl)oxy)pent-2-enoic acid
  参考文献：
  名称：

  Cis-Double Bond Formation by Thioesterase and Transfer by Ketosynthase in FR901464 Biosynthesis

  摘要：

  Modular polyketide synthases (PKSs) are well known to use ketosynthase (KS)-driven carbon-carbon bond formation, dehydratase-mediated dehydration to form double bonds, and product release by thioesterase (TE), all of which are regarded as the "canonical" roles for most polyketide biosyntheses. FR901464 is biosynthesized by a complex acyltransferase-less PKS system involving a nonterminal TE domain and several mutated KS domains. Here we demonstrate that this TE catalyzes the dehydration of the polyketide intermediate to yield a cis-double bond and a mutated KS transfers the nascent polyketide chain with only a cis-double bond to the downstream acyl carrier protein. These findings not only provide new insights into different enzymatic functions of PKS domains but also suggest an alternative strategy for cis-double bond formation during the polyketide assembly line.

  DOI：

  10.1021/ja500942y
• 作为产物：
  描述：

  methyl (S)-2-(tert-butyldimethylsiloxy)propanoate 在 二异丁基氢化铝 作用下， 以 二氯甲烷 、 甲苯 为溶剂， 反应 1.5h， 生成 ethyl (2Z,4S)-4-<(tert-butyldimethylsilyl)oxy>-2-pentenoate
  参考文献：
  名称：

  构象效应对大环INOC反应的区域选择性的作用：（+）-布雷菲德菌素A的两个新的不对称总合成。

  摘要：

  我们已经了解到构象效应对在我们的（+）-布雷菲德菌素A合成中观察到的大环分子内腈氧化物环加成反应的区域选择性的作用。在该区域化学研究的过程中，我们开发了两种新颖的立体选择性和区域选择性方案，用于全合成（+）-布雷菲德菌素A（即分子内一氧化氮环加成异构化和分子间一氧化氮环加成环封闭复分解策略）。

  DOI：

  10.1021/jo010744a

文献信息

• Intramolecular nitrile oxide cycloaddition on chiral olefins: a stereocontrolled approach to β-ketol precursors
  作者：Rita Annunziata、Mauro Cinquini、Franco Cozzi、Giulio Dondio、Laura Raimondi

  DOI：10.1016/s0040-4020(01)86823-x

  日期：——

  The intramolecular nitrile oxide cycloaddition reaction on chiral (E) and (Z) olefins featuring a sulphur atom along the carbon chain connecting dipole and dipolarophile occurs with poor to excellent anti stereoselectivity, which is mainly affected by the substitutents at the allylic stereocenter. The possibility of converting the cycloadducts into stereoisomerically pure β-ketols has been established

  沿连接偶极子和亲偶极子的碳链上具有硫原子的手性（E）和（Z）烯烃的分子内腈氧化物环加成反应发生时，其抗立体选择性差到极佳，这主要受烯丙基立体中心的取代基影响。在一种情况下，已经确定了将环加合物转化为立体异构纯的β-酮醇的可能性。
• Chiron approach towards optically pure <b>γ</b>-valerolactone from alanine
  作者：Rajender Datrika、Srinivasa Reddy Kallam、Rambabu Katta、Vidavalur Siddaiah、T. V. Pratap

  DOI：10.1080/00397911.2018.1491993

  日期：2018.11.2

  Abstract A concise synthesis of both enantiomers of γ-valerolactone has been developed from commercially available Alanine. The key steps in the synthesis of these γ-Lactones are DIBAL-H reduction of ester (9) followed by in situ Wittig reaction with EtO2CCH = PPh3 ylide (13) (Z/E = 1: 3.5) and one pot lactonization triggered by deprotection of O-TBS ether (14). Graphical Abstract

  摘要 γ-戊内酯的两种对映异构体的简明合成已从市售的丙氨酸中开发出来。合成这些 γ-内酯的关键步骤是酯 (9) 的 DIBAL-H 还原，然后是与 EtO2CCH = PPh3 叶立德 (13) (Z/E = 1: 3.5) 的原位 Wittig 反应和一锅内酯化O-TBS 醚 (14) 的脱保护。图形概要
• Diastereoselective synthesis of enantiopure 5-[2-(alkoxyalkyl)-1-(hydroperoxypropyl)]-3-alkoxycarbonyl-2-alkyl furans
  作者：Alessandra Lattanzi、Francesco Sagulo、Arrigo Scettri

  DOI：10.1016/s0957-4166(99)00187-1

  日期：1999.5

  The diastereoselective approach to enantiomerically pure furyl hydroperoxides of general type 1 has been accomplished starting from (S)-(-)-ethyl lactate. In the first part of the synthesis the alkylating reagents 7a,b were efficiently produced to be used in the second part for a 4-step known methodology to obtain furyl hydroperoxides. The most relevant transformation of the synthesis is the first reported diastereoselective iodoenoletherification of 2-acetyl-4-heptenoate esters 8a,b possessing a phi-chiral center. Furthermore, the final radical oxidation performed on (E)-5-alkylidene-4,5-dihydrofurans 11a,b led to formation of hydroperoxides (S,S)-12a,b in a diastereocontrolled manner due to 1,2-asymmetric induction. (C) 1999 Elsevier Science Ltd. All rights reserved.
• Chemoenzymatic One-Pot Synthesis of γ-Butyrolactones
  作者：Margarete Korpak、Jörg Pietruszka

  DOI：10.1002/adsc.201100110

  日期：2011.6

  AbstractThe synthesis of enantio‐ and diastereomerically pure γ‐butyrolactones is described using a one‐pot, two‐enzyme cascade. Ethyl 2‐methyl‐4‐oxopent‐2‐enoate (2) was reduced selectively first in a 1,4‐reduction using the old yellow enzyme (OYE1) [EC 1.6.99.1] and consecutively in a 1,2‐reduction by an alcohol dehydrogenase [EC 1.1.1.2].
• Diastereoselective Allylations of Allyl−Propargyl Hybrid Cations:  Synthesis of Conjugated 1,5-Dien-7-yne Frameworks Bearing C(4)-Stereogenic Centers
  作者：Teruhiko Ishikawa、Toshiaki Aikawa、Yumiko Mori、Seiki Saito

  DOI：10.1021/ol049847g

  日期：2004.4.1

  Chiral C(4)-substituted (E)- or (Z)-1-alkynyl-1-trimethylsilyloxy-2-butene systems provide anti-(Z) or syn-(Z) conjugated dienyne, with a very high level of stereocontrol, on treatment with (BF3OEt2)-O-. in CH2Cl2 at -50 degreesC in the presence of allyltrimethylsilane. The Cieplak conformation for (E)-substrates and neighboring-group participation for (2)-substrates are considered to be responsible for the stereochemical consequences.