(E)-hepta-2,6-dienal | 83085-82-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (E)-hepta-2,6-dienal
• 英文别名: (2E)-hepta-2,6-dienal
• CAS: 83085-82-9
• 化学式: C₇H₁₀O
• 分子量: 110.156
• InChiKey: PTWMQFJQDUYEGQ-AATRIKPKSA-N

物化性质

• 沸点：
  165.1±9.0 °C(Predicted)
• 密度：
  0.846±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  8
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (E)-hepta-2,6-dienal 在 aluminum tris(2,6-diphenylphenoxide) 、 RuCl2(1,3-dimesityl-imidazolidin-2-yl)(PCy3)(=CHPh) 、 甲醇 、 sodium tetrahydroborate 、 草酰氯 、 二异丁基氢化铝 、 二甲基亚砜 、 三乙胺 、 lithium bromide 作用下， 以 四氢呋喃 、 hexanes 、 乙醚 、 二氯甲烷 、 乙腈 为溶剂， 反应 10.0h， 生成 (E)-7-benzenesulfonyl-3-(2-bromo-ethyl)-2,2-dimethyl-hept-6-enal
  参考文献：
  名称：

  级联环化，偶极环加成桥三环胺相关的虎皮楠生物碱

  摘要：

  醛与伯胺的串联一锅法反应包括缩合，然后环化（N-烷基化），然后分子内偶极环加成所得的硝酮或甲亚胺叶立德，合成了桥连的三环胺。使用羟胺反应最成功，当双极性亲和剂是不饱和酯时，N-O键的还原和内酰胺的环化提供了yuzurimine，daphnilactone B和bukittinggine型Daphniphyllum生物碱的核心环系统。

  DOI：

  10.1021/ol102961x
• 作为产物：
  描述：

  methyl (2-ethenyl-4-pentenoate) 在 草酰氯 、 二异丁基氢化铝 、 二甲基亚砜 、 三乙胺 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 反应 16.75h， 生成 (E)-hepta-2,6-dienal
  参考文献：
  名称：

  Total Syntheses of (−)-Grandinolide and (−)-Sapranthin by the Sharpless Asymmetric Dihydroxylation of Methyltrans-3-Pentenoate: Elucidation of the Stereostructure of (−)-Sapranthin

  摘要：

  Methyl trans-3-pentenoate (7) was converted into the cis-substituted gamma-lactone 8 in a single step with 78 % ee. The derived enolate dilithio-8 was alkylated trans-selectively with primary iodoalkanes. with 1-iodobutane dilithio-8 afforded, after esterification with isovaleroyl chloride, the epi-blast mycinone 9, Dilithio-8 gave (-)-grandinolide (11) with 1-iodo-19-phenylnonadecane (20), A third trans-selective alkylation of dilithio-8 was undertaken with 16-iodo-1.5-hexadecadiene-7,9-diyne (21). This gave the gamma-lactone 12. which had the published relative configuration of (-)-sapranthin but different spectroscopic data, When the OH group of lactone 8 was inverted (to hydroxylactone 40) and the derived enolate dilithio-40 alkylated with iodide 21, lactone 41 resulted, Its H-1 and C-13 NMR spectra and the sign and value of optical rotation coincide with the data of natural sapranthin, These findings establish that (-)-sapranthin possesses the relative and absolute configuration of stereoformula 41. The synthesis of iodide 21 was performed via the dienoic carboxylic ester trans-23 which stemmed from the Claisen-Ireland rearrangement (27 --> 28/29)/esterification (28/29 --> 26)/Cope rearrangement (26 - 23) sequence shown in Scheme 5.

  DOI：

  10.1002/(sici)1521-3765(19981102)4:11<2342::aid-chem2342>3.0.co;2-q

文献信息

• Aza-Morita–Baylis–Hillman-type reactions: highly enantioselective organocatalytic addition of unmodified α,β-unsaturated aldehydes to N-Boc protected imines
  作者：Jan Vesely、Pawel Dziedzic、Armando Córdova

  DOI：10.1016/j.tetlet.2007.07.154

  日期：2007.9

  Highly enantioselective catalytic routes to Boc protected aza-Morita–Baylis–Hillman-type products are presented. The organocatalytic asymmetric reactions between unmodified α,β-unsaturated aldehydes and N-Boc protected aryl imines proceed with excellent chemo- and enantioselectivity to give the corresponding compounds in good yields with 97–99% ee.

  提出了对Boc保护的aza-Morita-Baylis-Hillman型产品的高度对映选择性催化路线。未修饰的α，β-不饱和醛与N - Boc保护的芳基亚胺之间的有机催化不对称反应具有出色的化学和对映选择性，可提供产率为97-99％ee的相应化合物。
• Temporary Generation of a Cyclopropyl Oxocarbenium Ion Enables Highly Diastereoselective Donor-Acceptor Cyclopropane Cycloaddition
  作者：Juliette Sabbatani、Nuno Maulide

  DOI：10.1002/anie.201601340

  日期：2016.6.1

  tetrahydrofurans display three new chiral centers formed with highly diastereoselectivity. This method is stereocomplementary to most previously reported cycloadditions of malonate diesters, relies on the transient generation of cyclopropyl oxocarbenium ions, proceeds under mild conditions, and is based on the concept of temporary activation of an otherwise inert protecting group.

  开发了一种新型的正式的环丙基缩醛和醛的[3 + 2]环加成反应，所得三取代四氢呋喃显示出具有高非对映选择性的三个新的手性中心。该方法与大多数先前报道的丙二酸酯二酯的环加成立体互补，依赖于在温和条件下进行的环丙基氧碳鎓离子的瞬时产生，并且基于暂时活化否则为惰性的保护基的概念。
• Organocatalytic diastereoselective dibromination of alkenes
  作者：Mingzhao Zhu、Shuangzheng Lin、Gui-Ling Zhao、Junliang Sun、Armando Córdova

  DOI：10.1016/j.tetlet.2010.03.043

  日期：2010.5

  A highly diastereoselective pyrrolidine-promoted dibromination of alkenes by combination of NBS and succinimide is presented. The pyrrolidine-mediated dibromination of alkenes is higly anti-selective and gives the corresponding products in moderate to high yields and up to >25:1 dr.

  提出了NBS和琥珀酰亚胺的组合的高度非对映选择性的吡咯烷促进的烯烃二溴化。烯烃的吡咯烷-介导的二溴化是higly抗-选择性，并给出了相应的产品在较高产率和高达> 25：1个博士。
• Asymmetric Aza-Morita-Baylis-Hillman-Type Reactions: The Highly Enantioselective Reaction between Unmodified α,β- Unsaturated Aldehydes and N-Acylimines by Organo-co-catalysis
  作者：Sylva Číhalová、Pawel Dziedzic、Armando Córdova、Jan Veselý

  DOI：10.1002/adsc.201000951

  日期：2011.5.9

  (MBH)‐type reaction between N‐carbamate‐protected imines and α,β‐unsaturated aldehydes has been developed. The organic co‐catalytic system of proline and 1,4‐diazabicyclo[2.2.2]octane (DABCO) enables the asymmetric synthesis of the corresponding N‐Boc‐ and N‐Cbz‐protected β‐amino‐α‐alkylidene‐aldehydes in good to high yields and up to 99% ee. In the case of aza‐MBH‐type addition of enals to phenylprop‐2‐ene‐1‐imines

  高对映选择性的有机助催化氮杂森田-的Baylis-希尔曼（MBH）型之间的反应ñ -氨基甲酸酯保护的亚胺和α，β不饱和醛已经研制成功。脯氨酸和1,4-二氮杂双环[2.2.2]辛烷（DABCO）的有机共催化体系可实现不对称合成相应的N - Boc-和N -Cbz保护的β-氨基-α-亚烷基-醛良品率高，ee高达99％。在苯丙-2-烯-1-亚胺的氮杂-MBH型加成反应中，助催化反应具有出色的1,2-选择性。有机-共催化的氮杂-MBH型反应也可以通过将α，β-不饱和醛直接高度对映选择性地添加到稳定的氮中来进行用氨基甲酸酯保护的α-酰胺基砜可得到相应的β-氨基-α-亚烷基醛，ee最高可达99％。有机-共催化的氮杂-MBH型反应也是近对映体纯的β-氨基-α-亚烷基-氨基酸和β-氨基-α-亚烷基-内酰胺（99％ee）的快速入口。还讨论了手性胺和DABCO共催化的aza-MBH型反应的机理和立体化学。
• 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。