ethyl (R,E)-4-(tert-butyldimethylsilyloxy)pent-2-enoate | 151122-17-7

• 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: ethyl (R,E)-4-(tert-butyldimethylsilyloxy)pent-2-enoate
• 英文别名: ethyl (E,4R)-4-[tert-butyl(dimethyl)silyl]oxypent-2-enoate
• CAS: 151122-17-7
• 化学式: C₁₃H₂₆O₃Si
• 分子量: 258.433
• InChiKey: JIPMHCMBHMJNGC-PBQZMEPESA-N

物化性质

• 沸点：
  285.5±23.0 °C(predicted)
• 密度：
  0.914±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.52
• 重原子数：
  17
• 可旋转键数：
  7
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.77
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  ethyl (R,E)-4-(tert-butyldimethylsilyloxy)pent-2-enoate 在 四丁基氟化铵 作用下， 以 四氢呋喃 为溶剂， 生成 ethyl (S)-(+)-(E)-4-hydroxy-2-pentenoate
  参考文献：
  名称：

  氨基酮的立体选择性烯丙基烷基化及其在高官能化哌啶合成中的应用。

  摘要：

  螯合的酮烯酸酯是烯丙基烷基化的优良亲核试剂。烯丙基部分上的吸电子基团允许随后的分子内迈克尔加成产生具有多达五个立体异构中心的哌啶。

  DOI：

  10.1002/chem.202000051
• 作为产物：
  描述：

  反式-4-氧基-2-丁烯酸乙酯 在 咪唑 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 生成 ethyl (R,E)-4-(tert-butyldimethylsilyloxy)pent-2-enoate
  参考文献：
  名称：

  Conformational study of chiral alkenes: the influence of protective groups on the relative stability of ground-state rotational isomers

  摘要：

  A variable temperature NMR study shows that a protective group on the hydroxy function of a chiral allylic alcohol can either enhance or counter the influence of the vinyl substituent on the ground-state (GS) conformations. If the allylic hydroxy is protected as a methyl ether, the CH-eclipsed form I becomes favored to a greater degree for normal chiral alkenes. Furthermore, conformer I becomes preferred even for the gamma-hydroxy-alpha,beta-unsaturated esters, which normally favor the CO-eclipsed form (II). On the other hand, the tert-butyldimethylsilyl (TBDMS) ether enhances the preference for conformer II for the gamma-hydroxy-alpha,beta-unsaturated esters and diminishes the preference for the CH-eclipsed form of normal chiral alkenes. These facts are explained by the size of the allylic oxygen lone pairs.

  DOI：

  10.1021/jo00077a023

文献信息

• Total Synthesis of a 6,6-Spiroketal Metabolite, Dinemasone A
  作者：Chada Raji Reddy、Boinapally Srikanth、Uredi Dilipkumar、Kakita Veera Mohana Rao、Bharatam Jagadeesh

  DOI：10.1002/ejoc.201201246

  日期：2013.1

  The stereoselective total synthesis of dinemasone A has been accomplished. The key reactions, Sharpless asymmetric epoxidation, lithium-mediated epoxy alcohol opening, and double-intramolecular hetero-Michael addition, gave access to dinemasone A from lactic acid esters. The stereochemistry at the spiro carbon was determined using extensive NMR studies.

  已完成地尼马松A的立体选择性全合成。关键反应 Sharpless 不对称环氧化、锂介导的环氧醇开环和双分子内杂迈克尔加成，可以从乳酸酯中获得地尼松 A。使用广泛的 NMR 研究确定了螺碳的立体化学。
• 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
• Role of Conformational Effects on the Regioselectivity of Macrocyclic INOC Reactions:  Two New Asymmetric Total Syntheses of (+)-Brefeldin A^,¹
  作者：Deukjoon Kim、Jongkook Lee、Phil Jong Shim、Joong Inn Lim、Takayuki Doi、Sanghee Kim

  DOI：10.1021/jo010744a

  日期：2002.2.1

  regioselectivity of the macrocyclic intramolecular nitrile oxide cycloaddition observed in our (+)-brefeldin A synthesis. During the course of this regiochemical study, we have developed two novel stereoselective and regioselective schemes for total synthesis of (+)-brefeldin A (i.e. intramolecular nitrile oxide cycloaddition-isomerization and intermolecular nitrile oxide cycloaddition-ring closing metathesis

  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）。
• Synthesis of a C1–C11 fragment of Zincophorin using planar chiral, neutral π-allyl iron complexes
  作者：John P. Cooksey

  DOI：10.1039/c3ob40894a

  日期：——

  A key step in the synthesis of a C1–C11 fragment of the ionophore antibiotic Zincophorin involves the addition of an α-alkoxyalkylcopper(I) reagent to a planar chiral, neutral π-allyl iron complex. The key allylic alkylation reaction is highly regio- and stereoselective with addition taking place at the γ-position anti to the metal centre.

  合成离子载体抗生素Zincophorin的C1-C11片段的关键步骤涉及将α-烷氧基烷基铜（I）试剂添加到平面手性中性π-烯丙基铁络合物中。关键烯丙基烷基化反应是高度区域选择性和立体选择性的配加在γ位发生反到金属中心。
• Total Synthesis and Determination of the Absolute Configuration of Berkeleylactone I
  作者：Sudip Mandal、Dora Mahananda、Dileep Paladugu、Barla Thirupathi

  DOI：10.1021/acs.joc.4c00178

  日期：2024.3.15

  Herein, we report the first total synthesis of berkeleylactone I and its 12S diastereomer. Consequently, this chemical synthesis allowed us to establish the unknown absolute stereochemistry at the C-12 center as 12R, which was unidentified by the isolation group. This synthetic approach includes several critical reactions, such as the Sharpless asymmetric dihydroxylation, Baran’s Ni-catalyzed alkyl–alkyl

  在此，我们报道了伯克内酯 I 及其 12 S非对映体的首次全合成。因此，这种化学合成使我们能够在 C-12 中心建立未知的绝对立体化学，即 12 R ，这是分离组无法识别的。该合成方法包括几个关键反应，例如 Sharpless 不对称二羟基化、Baran 镍催化的烷基-烷基交叉偶联反应、Brown 烯丙基化、Mitsunobu 反应和闭环复分解反应等关键步骤。