1-(methoxycarbonyl)-1,6-heptadiene | 51148-80-2

• 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: 1-(methoxycarbonyl)-1,6-heptadiene
• 英文别名: methyl (E)-octa-2,7-dienoate；methyl (E)-2,7-octadienoate；methyl 2,7-octadienoate；Methyl-2,7-octadienoat；methyl (2E)-octa-2,7-dienoate
• CAS: 51148-80-2
• 化学式: C₉H₁₄O₂
• 分子量: 154.209
• InChiKey: ACOLHUUSSOODOP-BQYQJAHWSA-N

物化性质

• 沸点：
  64-65 °C(Press: 1 Torr)
• 密度：
  0.910±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  11
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.44
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  1-(methoxycarbonyl)-1,6-heptadiene 在 咪唑 、 四氧化锇 、 N-甲基吲哚酮 作用下， 以 二氯甲烷 、 水 、 丙酮 为溶剂， 生成 (E)-8-(tert-Butyl-dimethyl-silanyloxy)-7-hydroxy-oct-2-enoic acid methyl ester
  参考文献：
  名称：

  A simple asymmetric synthesis of cis-2,6-disubstituted tetrahydropyran acetic acid derivatives

  摘要：

  A new asymmetric synthesis of functionalised cis-2,6-disubstituted tetrahydropyran acetic acids is described. The utility of the procedure is illustrated by the synthesis of (+) and (-)-(cis-6-methyltetrahydropyran-2-yl)acetic acid, a glandular secretion of the civet cat (Viverra civetta). (C) 1997, Elsevier Science Ltd.

  DOI：

  10.1016/s0040-4039(96)02483-5
• 作为产物：
  描述：

  methyl 7-hydroxyhept-2-enoate 在 正丁基锂 、 pyridinium chlorochromate 作用下， 以 二氯甲烷 为溶剂， 生成 1-(methoxycarbonyl)-1,6-heptadiene
  参考文献：
  名称：

  Tandem Inter [4 + 2]/Intra [3 + 2] Cycloadditions. 17. The Spiro Mode. Efficient and Highly Selective Synthesis of Azapropellanes

  摘要：

  A new variant of the tandem inter [4 + 2]/intra [3 + 2] nitroalkene cycloaddition has been developed. Intermolecular [4 + 2] cycloaddition of a 2-nitroalkene (bearing an unsaturated ester moiety, the dipolarophile) with a vinyl ether produces a cyclic nitronate substituted at C(3) wherein the only stereogenic center is the anomeric carbon C(6). Since the dipolarophile is attached to a tether extending from the C(3) of the nitronate (a-carbon of the nitroalkene), the intramolecular [3 + 2] cycloaddition affords a spiro tricyclic nitroso acetal. The cycloaddition proceeds smoothly for three- and four-atom tethers to afford five- and six-membered rings. Both E- and Z-unsaturated esters serve well as dipolarophiles, but the E-isomers react more selectively. Hydrogenolysis of the nitroso acetals affords the spiro tricyclic alpha-hydroxy lactams in good yield. Remarkably high levels of asymmetric induction are observed with the use of a chiral vinyl ether derived from (1R,2S)-2-phenylcyclohexanol. The origin of asymmetric induction is a combination of the established face selectivity of the enol ether and the preference for a distal fold of the tether away from the: substituent on the anomeric carbon. The scope and limitations of this transformation and an analysis of the origin of stereoselectivity are provided.

  DOI：

  10.1021/jo9719057

文献信息

• Absolute configuration of the spiroacetal portion of zooxanthellatoxin-A
  作者：Hideshi Nakamura、Kuniaki Sato、Akio Murai

  DOI：10.1016/0040-4039(96)01645-0

  日期：1996.9

  By synthesizing the MTPA ester 11, an enantiomer of the degradation product 1, the absolute configuration of the spiroacetal portion (C79C95) of zooxanthellatoxin-A was determined to be 81R, 85R, and 93S.

  通过合成MTPA酯11，降解产物的对映体1，zooxanthellatoxin-A的螺缩醛部分（C79C95）的绝对构型被测定为81 - [R，85 - [R ，和93小号。
• Mechanistic Interrogation of Co/Ni-Dual Catalyzed Hydroarylation
  作者：Sophia L. Shevick、Carla Obradors、Ryan A. Shenvi

  DOI：10.1021/jacs.8b06458

  日期：2018.9.26

  mechanistic model of this reaction through the use of reaction progress kinetic analysis (RPKA), radical clock experiments, and stoichiometric studies. Through exclusion of competing hypotheses, we conclude that the reaction proceeds through an unprecedented alkylcobalt to nickel direct transmetalation. Demonstration of catalytic alkene prefunctionalization, via spectroscopic observation of an organocobalt

  钴/镍双催化末端烯烃与碘芳烃的加氢芳基化利用容易获得的起始材料构建了复杂性，并且高度优先选择马尔可夫尼科夫（支化）产物。在这里，我们通过使用反应进程动力学分析（RPKA）、自由基时钟实验和化学计量研究，提出了该反应的机理模型。通过排除竞争假设，我们得出结论，该反应通过前所未有的烷基钴到镍的直接金属转移进行。通过有机钴物质的光谱观察，催化烯烃预官能化的演示将这种 Csp2-Csp3 交叉偶联方法与传统的金属转移过程（采用化学计量的有机金属亲核试剂）和有机卤化物跨镍的双金属氧化加成区别开来，描述为自由基断裂和随后的烷基自由基在第二个镍中心捕获。对反应的深入理解导致了优化的加氢芳基化程序，排除了外源氧化剂，证明金属转移是净氧化还原中性的。钴催化烯烃预官能化以及通过直接金属转移与镍催化循环的接触提供了一个新平台，以预备有用的方式融合这两个丰富的化学领域。
• Cross-Metathesis of the Vinyl Group on Tetrapyrrolic Macrocycles: Reactivity, Selectivity, and Mechanism
  作者：Xin Liu、Ethan Sternberg、David Dolphin

  DOI：10.1021/jo8007989

  日期：2008.9.1

  To find a general strategy for modifying the peripheral structure of vinylchlorin and porphyrin substrates, cross-metathesis on the vinyl group of these tetrapyrrolic macrocycles was investigated. The N-heterocyclic carbene-containing ruthenium complex 3 efficiently catalyzed the cross-metathesis (CM) of vinylchlorins and vinylporphyrins with a variety of olefins in high E-stereoselectivity. Different

  为了找到改变乙烯基氯和卟啉底物外围结构的一般策略，研究了这些四吡咯大环乙烯基上的交叉复分解。含N-杂环卡宾的钌配合物3以高的E-立体选择性有效地催化了乙烯基氯和乙烯基卟啉与多种烯烃的交叉复分解（CM）。烯烃上的不同取代基极大地影响了反应。二氢卟酚比卟啉具有更高的反应性（以游离碱计），但相应的锌络合物显示出更高的活性。研究了反应机理，并将选择性CM的经验模型应用于我们的研究以指导进一步的反应。
• Process for synthesizing zearalanone and related compounds
  申请人：Commercial Solvents Corporation

  公开号：US03957825A1

  公开（公告）日：1976-05-18

  This invention provides a new synthesis for zearalanone and for related compounds having more or fewer carbon atoms in the non-aromatic ring than does zearalanone, which related compounds and zearalanone are represented by the formula ##SPC1## Wherein X is an integer having a value from 2 to 6 inclusive and Y is an integer having a value from 2 to 8 inclusive. It also provides for new methods of making compounds useful in the synthesis of zearalanone and related compounds. The new compounds useful as intermediates are 2,7-octadienoic acid; methyl 2,7-octadienoate; sodium ethyl 6-(4-pentenyl)-.beta.-dihydroresorcylate; ethyl 6-(4-pentenyl)-.beta.-dihydroresorcylate; sodium methyl 6-(4-pentenyl)-.beta.-dihydroresorcylate; methyl 6-(4-pentenyl)-.beta.-dihydroresorcylate; methyl 3-bromo-6-(4-pentenyl)-.beta.-dihydroresorcylate; methyl 6-(4-pentenyl)-.beta.-resorcylate; ethyl 6-(4-pentenyl)-.beta.-resorcylate; ethyl 6-(4-pentenyl)-.beta.-resorcylate dibenzyl ether; and 4-penten-2-yl 6-(4-pentenyl)-.beta.-resorcylate dibenzyl ether.

  本发明提供了一种新的合成方法，用于制备Zearalanone及其非芳香环中比Zearalanone碳原子数更多或更少的相关化合物，其中这些相关化合物和Zearalanone由以下公式表示：##SPC1## 其中X是一个整数，其值为2到6，包括2和6，Y是一个整数，其值为2到8，包括2和8。它还提供了制备在Zearalanone和相关化合物的合成中有用的新化合物的方法。新的中间体化合物包括2,7-辛二烯酸；甲基2,7-辛二烯酸酯；乙基6-(4-戊烯基)-β-二氢雷司酸钠盐；乙基6-(4-戊烯基)-β-二氢雷司酸酯；甲基6-(4-戊烯基)-β-二氢雷司酸钠盐；甲基6-(4-戊烯基)-β-二氢雷司酸酯；甲基3-溴-6-(4-戊烯基)-β-二氢雷司酸酯；甲基6-(4-戊烯基)-β-雷司酸酯；乙基6-(4-戊烯基)-β-雷司酸酯；乙基6-(4-戊烯基)-β-雷司酸酯二苯甲醚；以及4-戊烯-2-基6-(4-戊烯基)-β-雷司酸酯二苯甲醚。
• Sterically Biased 3,3-Sigmatropic Rearrangement of Chiral Allylic Azides: Application to the Total Syntheses of Alkaloids
  作者：Sophie Lauzon、François Tremblay、David Gagnon、Cédrickx Godbout、Christine Chabot、Catherine Mercier-Shanks、Stéphane Perreault、Hélène DeSève、Claude Spino

  DOI：10.1021/jo800817p

  日期：2008.8.1

  We describe a tandem Mitsunobu/3,3-sigmatropic rearrangement of allylic azides on a chiral auxiliary system that favors one regioisomer thanks to its exceptional steric bias. The sequence may be completed by the oxidative cleavage of the auxiliary or by a ring-closing metathesis reaction that produces a carboor heterocycle directly and a recyclable form of the chiral auxiliary. Applications of the methodology to the total synthesis of (+)-coniine, (+)-lentiginosin, and (+)-pumiliotoxin C are reported.