hepta-1,6-dien-3-yl acetate | 56505-44-3

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: hepta-1,6-dien-3-yl acetate
• CAS: 56505-44-3
• 化学式: C₉H₁₄O₂
• 分子量: 154.209
• InChiKey: ASHKKRNNCIOOKK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 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：

  hepta-1,6-dien-3-yl acetate 生成 (E)-4,8-nonadienoic acid
  参考文献：
  名称：

  Rossi, Renzo; Carpita, Adriano; Quirici, Maria Grazia, Gazzetta Chimica Italiana, 1981, vol. 111, # 5/6, p. 173 - 180

  摘要：

  DOI：
• 作为产物：
  描述：

  4-戊烯醛 在 三乙胺 作用下， 以 四氢呋喃 为溶剂， 反应 1.0h， 生成 hepta-1,6-dien-3-yl acetate
  参考文献：
  名称：

  烷基取代的烯丙乙酸酯与仲胺的区域选择性和对映选择性铱催化胺化

  摘要：

  由 ( S )-tol-BINAP 改性的稳定的空气稳定环金属化 π-烯丙铱C , O-苯甲酸酯催化脂肪仲胺与外消旋烷基取代的烯丙乙酸酯的反应，提供具有高水平对映选择性的烯丙胺化产物。尽管形成了更高取代度的 C-N 键，但仍观察到完全支化的区域选择性。

  DOI：

  10.1021/acs.orglett.1c04135

文献信息

• Enantioselective Iridium-Catalyzed Allylic Alkylation of Racemic Branched Alkyl-Substituted Allylic Acetates with Malonates
  作者：Tian-Yuan Zhang、Yi Deng、Kun Wei、Yu-Rong Yang

  DOI：10.1021/acs.orglett.0c04309

  日期：2021.2.5

  The regio- and enantioselective allylic substitution of branched alkyl-substituted allylic acetates employing malonates has been achieved through a process that calls for Krische’s π-allyliridium C,O-benzoate catalyst. The protocol reported herein can be applied to a diverse set of branched alkyl substrates that are generally not well tolerated in the other two types of Ir-catalyzed allylation.

  使用丙二酸酯的支链烷基取代的烯丙基乙酸酯的区域和对映选择性烯丙基取代是通过要求Krische的π-烯丙基铱C，O-苯甲酸酯催化剂的方法实现的。本文报道的方案可应用于通常在其他两种类型的Ir催化的烯丙基化中不能很好耐受的各种支链烷基底物上。
• Enantioselective Iridium-Catalyzed Allylation of Nitroalkanes: Entry to β-Stereogenic α-Quaternary Primary Amines
  作者：Woo-Ok Jung、Binh Khanh Mai、Brian J. Spinello、Zachary J. Dubey、Seung Wook Kim、Craig E. Stivala、Jason R. Zbieg、Peng Liu、Michael J. Krische

  DOI：10.1021/jacs.1c05212

  日期：2021.6.30

  The first systematic study of simple nitronate nucleophiles in iridium-catalyzed allylic alkylation is described. Using a tol-BINAP-modified π-allyliridium C,O-benzoate catalyst, α,α-disubstituted nitronates substitute racemic branched alkyl-substituted allylic acetates, thus providing entry to β-stereogenic α-quaternary primary amines. DFT calculations reveal early transition states that render the

  描述了铱催化烯丙基烷基化中简单硝基亲核试剂的首次系统研究。使用tol-BINAP修饰的π-烯丙基铱C , O-苯甲酸酯催化剂，α,α-二取代硝基化合物取代外消旋支链烷基取代的烯丙基乙酸酯，从而提供β-立体异构α-季伯胺的入口。 DFT 计算揭示了早期过渡态，使反应对空间效应和非对映手性铱 π-烯丙基络合物的明显反式效应不太敏感，从而促进了拥挤的三级-四级 C-C 键的形成。
• In situ tandem allylic acetate isomerisation-ring closing metathesis: 1,3-dimesityl-4,5-dihydroimidazol-2-ylidene ruthenium benzylidenes and palladium(0)–phosphine combinations
  作者：D.Christopher Braddock、Ai Matsuno

  DOI：10.1016/s0040-4039(02)00526-9

  日期：2002.4

  benzylidenes as olefin metathesis pre-catalysts in conjunction with palladium(0)–phosphine combinations allows tandem in situ allylic acetate isomerisation–ring closing metathesis reactions to occur. The tandem reaction can either be performed on separate substrates in the same pot, or on substrates containing both allylic acetate and diene functionality.

  1,3-二甲杂1-4、5-二氢咪唑-2-亚甲基钌苄叉烯与钯（0）-膦组合使用作为烯烃复分解的预催化剂，可以串联进行原位烯丙基乙酸酯异构化-封闭的复分解反应发生。串联反应可以在同一罐中的单独底物上进行，也可以在同时包含乙酸烯丙酯和二烯官能度的底物上进行。
• The Reaction of Open-chain Unconjugated Dienes with Palladium Acetate. Dependence of the Products on Disposition of the Two Double Bonds
  作者：Nobuo Adachi、Kiyoshi Kikukawa、Makoto Takagi、Tsutomu Matsuda

  DOI：10.1246/bcsj.48.521

  日期：1975.2

  The reaction of open-chain unconjugated dienes with palladium acetate in acetic acid was investigated with particular reference to the behavior of the two double bonds in the course of the acetoxylation. 1,5-Hexadiene produced 3-acetoxymethylenecyclopentane (64%), but 2,6-octadiene bearing two terminal methyl groups gave open-chain acetoxylated products: 3-acetoxy-1,6-octadiene (46%) and 7-acetoxy-2

  特别参考两个双键在乙酰氧基化过程中的行为，研究了开链非共轭二烯与乙酸钯在乙酸中的反应。1,5-己二烯生成 3-乙酰氧基亚甲基环戊烷 (64%)，但带有两个末端甲基的 2,6-辛二烯生成开链乙酰氧基化产物：3-乙酰氧基-1,6-辛二烯 (46%) 和 7-乙酰氧基- 2,5-辛二烯 (47%)。发现 1,6-庚二烯和二烯丙基醚的反应通过异常反马尔科夫尼科夫加成进行，得到顺式和反式 1-乙酰氧基-1,6-庚二烯 (63%) 和 γ-乙酰氧基烯丙基烯丙基醚 (84%)，分别。在 1,7-辛二烯的反应中没有观察到第二个双键的参与。通过假设 π 的形成，可以合理地解释这些二烯对醋酸钯的行为，
• Pd-Catalyzed Cycloisomerization to 1,2- Dialkylidenecycloalkanes. 1
  作者：Barry M. Trost、Gerald J. Tanoury、Mark Lautens、Chuen Chan、David T. MacPherson

  DOI：10.1021/ja00089a015

  日期：1994.5

  Enhancing synthetic efficiency requires the development of synthetic reactions that, to the extent possible, are simple additions wherein everything else is required only in catalytic amounts. The Alder ene reaction constitutes a classical reaction that meets this requirement that has much unrealized potential. A transition-metal-catalyzed version helps to increase that potential by permitting this reaction to proceed under mild conditions. A significant benefit of transition metal catalysis is the feasibility of diverting the reaction along pathways not feasible under thermal conditions. The synthesis of 1,3-dienes rather than 1,4-dienes is a very important diversion because of the utility of 1,3-dienes as reaction partners in the Diels-Alder reaction, another highly atom economical process. A catalyst derived from palladium acetate cycloisomerizes 1,6- and 1,7-enynes to dialkylidenecyclopentanes and -cyclohexanes. 1,3-Diene formation is favored over the Alder ene process by both steric and electronic effects. The reaction is highly chemoselective-tolerating a wide diversity of functionality including hydroxyl groups, ketones, esters, alkynyl and enol ethers, alkynyl and vinyl silanes, and enones. Many of the substrates are available by palladium-catalyzed alkylation reactions-highlighting the effectiveness of palladium catalyzed methodology in organic synthesis. The atom-economical nature of these reactions combined with the Diels-Alder reaction permit butadiene and dimethyl propargylmalonate to be molded into a polyhydro-as-indacene. The mechanism of this reaction may involve a tautomerization of an enyne-Pd(+2) complex to a pallada(+4)cyclopentene intermediate as a key step.