tert-butyl 3-oxooct-7-enoate | 171112-54-2

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 酮酸及其衍生物
• 英文名称: tert-butyl 3-oxooct-7-enoate
• 英文别名: tert-butyl 3-oxo-7-octenoate
• CAS: 171112-54-2
• 化学式: C₁₂H₂₀O₃
• 分子量: 212.289
• InChiKey: ABTIRNQTOLRHGM-UHFFFAOYSA-N

物化性质

• 沸点：
  271.4±23.0 °C(Predicted)
• 密度：
  0.954±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  15
• 可旋转键数：
  8
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  tert-butyl 3-oxooct-7-enoate 在 palladium on activated charcoal Grubbs catalyst first generation 、 氢气 、 1-羟基苯并三唑 、 盐酸-N-乙基-Nˊ-(3-二甲氨基丙基)碳二亚胺 、 三氟乙酸 作用下， 以 二氯甲烷 、 乙酸乙酯 、 乙腈 为溶剂， 生成 N-(3-oxo-10-phenyldecanoyl)-L-homoserine lactone
  参考文献：
  名称：

  Synthesis of Pseudomonas quorum-sensing autoinducer analogs and structural entities required for induction of apoptosis in macrophages

  摘要：

  The synthesis of the analogs of N-3-oxododecanoyl-L-homoserine lactone (1) and their structure-activity relationship for the apoptotic induction in macrophages, P388D1 cells, are described. It was revealed that the position of the oxo group in the acyl side chain in addition to the presence of the L-homoserine lactone unit is crucial for the apoptosis-inducing activity. Furthermore, the long acyl side chains with hydrophobic distal ends are preferable for the activity. (C) 2006 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.bmcl.2006.01.054
• 作为产物：
  描述：

  4-溴-1-丁烯 、 乙酰乙酸叔丁酯 在 正丁基锂 、 sodium hydride 作用下， 以 四氢呋喃 、 正己烷 、 paraffin 为溶剂， 反应 3.0h， 以58%的产率得到tert-butyl 3-oxooct-7-enoate
  参考文献：
  名称：

  自由基对手性 1,3-二恶英-4-酮的非对映选择性加成

  摘要：

  研究了自由基向 1,3-二恶英-4-酮 1a,b 和 2a,b 的分子间加成，其中 (-)-薄荷酮作为 2 位手性助剂加入。来自 1,3-二氧戊环、氧杂环戊烷和 2-丙醇的光化学产生的自由基被添加到更多暴露的 a 侧，具有高面部选择性。1,3-二氧戊环-2-基自由基向手性二恶英酮的分子内加成效率较低，并且从α-侧也具有较低的选择性。然而，有可能形成新的螺环化合物 22-27。具有不饱和侧链的 1,3-二恶英-4-ones 32a,b 被末端双键处的自由基攻击。在 32b 在 1,3-二氧戊环中辐照的情况下，在 1,3-二氧戊环-2-基的分子间加成之后发生环化反应，形成二螺环化合物 36。然而，二螺环化合物 40 的形成需要两个反应步骤，从 32b 和溴三氯甲烷的辐照开始。在 C-2 处具有不饱和侧链的非手性 1,3-dioxin-4-one 44 优先在 C-6 处受到 1,3-dioxolan-2-yl

  DOI：

  10.1002/(sici)1099-0690(199905)1999:5<1057::aid-ejoc1057>3.0.co;2-a

文献信息

• Practical and Robust Method for Regio- and Stereoselective Preparation of (<i>E</i>)-Ketene <i>tert</i>-Butyl TMS Acetals and β-Ketoester-derived <i>tert</i>-Butyl (1<i>Z</i>,3<i>E</i>)-1,3-Bis(TMS)dienol Ethers
  作者：Tomohito Okabayashi、Akira Iida、Kenta Takai、Yuuya Nawate、Tomonori Misaki、Yoo Tanabe

  DOI：10.1021/jo701456t

  日期：2007.10.1

  We developed an efficient, practical, robust method for the regio- and stereoselective preparation of (E)-ketene trimethylsilyl acetals (KSAs) derived from tert-butyl esters 1. The reaction was performed under convenient reaction conditions; LDA−TMSCl, 0−5 °C, and cyclopentyl methyl ether (CPME) solvent. Two kinds of (Z)- and (E)-KSAs derived from α-oxygen and α-nitrogen-substituted tert-butyl esters

  我们开发了一种高效，实用，鲁棒的方法，用于区域和立体选择性制备衍生自叔丁酯1的（E）-乙烯酮三甲基甲硅烷基乙缩醛（KSA）。反应在方便的反应条件下进行；LDA-TMSCl，0-5°C和环戊基甲基醚（CPME）溶剂。还分别以良好的产率获得了分别衍生自α-氧和α-氮取代的叔丁基酯的两种（Z）-和（E）-KSAs 。本协议已成功应用于有用但反应性强（β-酮基酯）衍生的叔丁基（1 Z，3 E）-1,3-二（TMS）二烯醇醚2。
• Phase-Transfer Catalyzed Asymmetric [4 + 1] Annulations for the Synthesis of Chiral 2,2-Disubstituted Tetrahydrothiophenes
  作者：Qi Yin、Xiaolu Wen、Yiwei Chen、Xiangnan Gong、Lin Hu

  DOI：10.1021/acs.orglett.1c02744

  日期：2021.10.1

  An efficient catalytic asymmetric [4 + 1] reaction, which features the use of simple β-keto esters as one-carbon nucleophiles and 5-succinimidothio-pent-2-enoates as four-atom bielectrophiles, has been developed in the presence of a bifunctional chiral phase-transfer catalyst. The new annulation provides a distinct protocol to access the functionalized 2-acyl-2-carboxyl tetrahydrothiophenes bearing

  一种高效的催化不对称 [4 + 1] 反应，其特点是使用简单的 β-酮酯作为单碳亲核试剂，使用 5-琥珀酰亚胺硫代-戊-2-烯酸酯作为四原子双亲电试剂，在双功能手性相转移催化剂。新的环化提供了一种独特的协议，以获取具有高非对映选择性和对映选择性的连续季和叔碳立体中心的官能化 2-酰基-2-羧基四氢噻吩。此外，制备的产物可以通过脱苯甲酰化和烷基化反应两个步骤容易地转化为手性 2-烷基-2-羧基四氢噻吩。
• A One-Pot Methodology for the Synthesis of the Yohimban Skeleton
  作者：Claudio Parra、Pablo Solís、Josep Bonjoch、Ben Bradshaw

  DOI：10.1055/s-0036-1589092

  日期：2017.9

  A simple and straightforward assembly of the yohimban skeleton was achieved by condensation of an acyclic β-keto ester with tryptamine, followed by consecutive cross metathesis and tandem cyclization reactions, leading to the formation of three new rings. The whole process was readily carried out in the one-flask providing a rapid entry to the pentacyclic scaffold of yohimbine alkaloids.

  通过无环 β-酮酯与色胺缩合，随后进行连续的交叉复分解和串联环化反应，形成三个新环，从而实现了育亨班骨架的简单直接组装。整个过程很容易在一个烧瓶中进行，提供快速进入育亨宾生物碱的五环支架。
• Intramolecular Photoaddition of Alkenes to Chiral 1,3-Dioxin-4-ones: Evidence for Effect of Pyramidalization on the Facial Selectivity
  作者：Nizar Haddad、Zehavit Abramovich

  DOI：10.1021/jo00126a045

  日期：1995.10

  Intramolecular photoaddition of alkenes to chiral 1,3-dioxin -4-ones 5 present, for the first time, examples with high facial selectivity in which the addition proceeds preferentially from the less exposed side (b-side) under kinetic control conditions. This unprecedented facial selectivity cannot be explained only on the basis of steric effects; however, it is consistent with the direction of pyramidalizaton in structure 3. It can be concluded that the geometry of the pyramidalized C-beta in the triplet excited dioxinones plays an important role in defining the facial selectivity in this reaction. However, steric effect cannot be neglected in rationalizing the facial selectivity as found by comparing the facial selectivity obtained in the irradiation of the studied compounds.
• A Tetramethoxybenzophenone as Efficient Triplet Photocatalyst for the Transformation of Diazo Compounds
  作者：Lourdes Pastor-Pérez、Christine Wiebe、Julia Pérez-Prieto、Salah-Eddine Stiriba

  DOI：10.1021/jo062426n

  日期：2007.2.1

  The aromatic ketone 2,2',4,4'-tetramethoxybenzophenone has a strong absorption band between 300 and 375 nm, and its pi,pi* triplet excited-state is selectively populated in methanol. Both facts make this aromatic ketone a versatile and efficient triplet photocatalyst for the transformation of alpha-diazo carbonyl compounds into mainly the cyclopropanation product.