(6E)-6,8-nonadienal | 78669-40-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (6E)-6,8-nonadienal
• 英文别名: (E)-nona-6,8-dienal；(E)-6,8-nonadienal；nona-6(E),8-dienal；6(E),8-nonadienal；6,8-nonadienal；(6E)-nona-6,8-dienal
• CAS: 78669-40-6
• 化学式: C₉H₁₄O
• 分子量: 138.21
• InChiKey: KFCWBYVPPYORPI-ONEGZZNKSA-N

物化性质

• 沸点：
  203.3±9.0 °C(Predicted)
• 密度：
  0.847±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  10
• 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：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (6E)-6,8-nonadienal 在 chromium dichloride 作用下， 以 四氢呋喃 为溶剂， 反应 3.0h， 生成 methyl 1,2,3,4,4aα,5,6,8aα-octahydronaphthalene-5β-carboxylate
  参考文献：
  名称：

  Stereochemical control in intramolecular Diels-Alder reactions with carbene complexes as ester synthons

  摘要：

  An evaluation of the intramolecular Diels-Alder reactions of Fischer carbene complexes was made for complexes which have an all-carbon tether between the diene and dienophile. Specifically, both the cis- and trans-isomers of the deca-2,7,9-trienyl carbene complexes (26-cis, 24-trans) and the undeca-2,8,10-trienyl carbene complexes (27-cis, 25-trans) were prepared and the rates and stereoselectivities of their intramolecular Diels-Alder reactions were in each case compared with those of the known reactions of their corresponding methyl esters. For the deca-2,7,9-trienyl complexes 24 and 26, the stereoselectivities are comparable to those observed for the Lewis-acid-catalyzed reactions of their corresponding methyl esters and much higher than the thermal reactions of the methyl esters which are completely unselective. The undeca-2,8,10-trienyl complex 25 undergoes intramolecular Diels-Alder reaction with a 93:7 endo/exo selectivity whereas the corresponding methyl ester 7 is known to give a 51:49 selectivity under thermal conditions and to fail with attempts at Lewis acid catalysis. The cis-substituted complex 27 also undergoes a selective reaction where the corresponding reaction of the ester fails. In addition no trace of isomerization of the cis-complex 27 could be observed during its cycloaddition. The triphenylphosphine and isopropoxy complexes 28-30 were prepared, and the stereoselectivity of their intramolecular Diels-Alder reactions is consistent with an s-trans conformation of the vinyl carbene funtionality in the transition state. In all cases the carbene complex cycloadducts can be oxidatively cleaved in high yield to their corresponding esters. The results show that the value of these complexes as synthons for esters is a result of tolerance of the carbene complex functional group to sensitive diene units which do not tolerate traditional Lewis acids utilized in accelerating intramolecular Diels-Alder reactions.

  DOI：

  10.1021/jo00061a008
• 作为产物：
  描述：

  6-氧代己酸甲酯 在 硫酸 、 silica gel 、 二异丁基氢化铝 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 0.17h， 生成 (6E)-6,8-nonadienal
  参考文献：
  名称：

  LiBF 4：一种用于分子内狄尔斯-阿尔德反应的温和的路易斯酸。

  摘要：

  已经研究了锂盐LiClO 4和LiBF 4在分子内Diels-Alder反应中作为路易斯酸催化剂的潜在用途。当使用LiClO 4时，未观察到三烯酮1的环加成。LiBF 4在室温下72小时内可定量提供顺式融合的环加合物。催化作用归因于BF 3的缓慢释放，而不是锂阳离子。

  DOI：

  10.1016/s0040-4039(00)74269-9

文献信息

• Asymmetric intramolecular Diels-Alder reactions of N-acyl-camphor-sultam trienes.
  作者：Wolfgang Oppolzer、Dominique Dupuis

  DOI：10.1016/s0040-4039(00)98228-5

  日期：1985.1

  Treatment of triene-imides 4 with EtAlCl2 at −20° gave crystalline cycloadducts 5 which furnished enantiomerically pure bicyclic alcohols 9 with regeneration of the chiral auxiliary.

  在-20°下用EtAlCl 2处理三烯酰亚胺4，得到结晶的环加合物5，其提供对映体纯的双环醇9并具有手性助剂的再生。
• Asymmetric intramolecular Diels-Alder reactions of sulfoximine-activated trienes
  作者：Donald Craig、Neil J. Geach、Christopher J. Pearson、Alexandra M.Z. Slawin、Andrew J.P. White、David J. Williams

  DOI：10.1016/0040-4020(95)00267-c

  日期：1995.5

  A series of N-substituted sulfoximidoyl-1,6,8-nonatrienes and 1,7,9-decatrienes were synthesised and subjected to thermal intramolecular Diels-Alder (IMDA) reactions to give diastereomeric mixtures of substituted bicyclo[4.3.0]nonanes and -[4.4.0]decanes. The reactions showed varying selectivities. Endo/exo selectivity was interpreted in terms of a combination of steric factors and the asynchronous

  合成了一系列的N-取代的亚磺酰亚胺基-1,6,8-壬烯和1,7,9-癸二烯，并进行热分子内Diels-Alder（IMDA）反应，得到取代的双环[4.3.0]壬烷的非对映异构体混合物和-[4.4.0]癸烷。反应显示出不同的选择性。内/外选择性是根据空间因素和环加成反应的异步性质的组合来解释的。通过考虑二烯在构象扩展的乙烯基亚砜亚胺二烯亲和体的较少受阻面上的进攻，可以合理化非对面选择性。
• Bis(oxazoline) and Bis(oxazolinyl)pyridine Copper Complexes as Enantioselective Diels−Alder Catalysts:  Reaction Scope and Synthetic Applications
  作者：David A. Evans、David M. Barnes、Jeffrey S. Johnson、Thomas Lectka、Peter von Matt、Scott J. Miller、Jerry A. Murry、Roger D. Norcross、Eileen A. Shaughnessy、Kevin R. Campos

  DOI：10.1021/ja991191c

  日期：1999.8.1

  the use of this chiral catalyst in more complex Diels−Alder processes, are described. Similarly, the cationic copper complex 9a, [Cu((S,S)-t-Bu-pybox)](SbF6)2, is effective in the Diels−Alder reactions of monodentate acrolein dienophiles while the closely related complex, 9d [Cu((S,S)-Bn-pybox)](SbF6)2, is the preferred Lewis acid catalyst for acrylate dienophiles in reactions with cyclopentadiene.

  已经研究了由双（恶唑啉）铜配合物催化的 Diels-Alder 反应的范围。特别是，[Cu((S,S)-t-Bu-box)](SbF6)2 (1b) 已被证明可以催化 3-propenoyl-2-oxazolidinone (2) 和一系列的 Diels-Alder 反应。具有高对映选择性的取代二烯。这种阳离子复合物也已成功用于类似分子内过程的催化。描述了 ent-Δ1-四氢大麻酚、ent-莽草酸和 isopulo'upone 的全合成，其特点是在更复杂的 Diels-Alder 过程中使用这种手性催化剂。类似地，阳离子铜配合物 9a，[Cu((S,S)-t-Bu-pybox)](SbF6)2，在单齿丙烯醛亲二烯体的 Diels-Alder 反应中是有效的，而密切相关的配合物 9d [Cu ((S,S)-Bn-pybox)](SbF6)2,
• The 1-Phenylsulfonylallenyl Terminus in Intramolecular Diels-Alder Reactions: Tether Length and Reactivity
  作者：James R. Bull、Richard S. Gordon、Roger Hunter

  DOI：10.1055/s-1999-2675

  日期：1999.5

  Methods are described for the synthesis of 1-phenylsulfonylalka-1,2,(n + 4),(n + 6)-tetraenes 5 (n = 2-4), and preliminary findings on their thermally-induced intramolecular cycloaddition behaviour are reported. The reaction of 5 (n = 4) is slow, and engages the unactivated π-bond, whereas those of 5 (n = 2 & 3) proceed readily and exo-selectively with dienophilic participation of the activated terminal π-bond, to give the expected [4 + 2] cycloadducts. The reactivity of 5 (n = 2) is particularly noteworthy since cycloaddition proceeds under exceptionally mild conditions.

  描述了1-苯磺酰基-1,2,(n+4),(n+6)-四烯5（n=2-4）的合成方法，并报道了它们热诱导的分子内环加成行为的初步研究结果。反应5（n=4）较慢，涉及未活化的π键，而5（n=2和3）的反应则迅速进行，且端位的活化π键参与亲双烯体作用，生成预期的[4+2]环加成产物。5（n=2）的反应活性特别值得注意，因为环加成反应在极为温和的条件下即可进行。
• A Novel Decalin-Based Bicyclic Scaffold for FKBP51-Selective Ligands
  作者：Xixi Feng、Claudia Sippel、Fabian H. Knaup、Andreas Bracher、Stefania Staibano、Maria F. Romano、Felix Hausch

  DOI：10.1021/acs.jmedchem.9b01157

  日期：2020.1.9

  inhibition of FKBP51 has emerged as possible novel treatment for diseases like major depressive disorder, obesity, chronic pain, and certain cancers. The current FKBP51 inhibitors are rather large, flexible, and have to be further optimized. By using a structure-based rigidification strategy, we hereby report the design and synthesis of a novel promising bicyclic scaffold for FKBP51 ligands. The structure-activity

  对FKBP51的选择性抑制已成为对诸如重度抑郁症，肥胖症，慢性疼痛和某些癌症等疾病的可能新疗法。当前的FKBP51抑制剂相当大，柔韧性，并且必须进一步优化。通过使用基于结构的刚性化策略，我们在此报告FKBP51配体的新型有前途的双环支架的设计和合成。结构活性分析表明，十氢化萘支架是FBKP51选择性选择性亚口袋的最佳部分。所得化合物保留了对FKBP51的高效力，并且与紧密同源的FKBP52相比具有出色的选择性。在这个新系列的高级配体的共晶体结构中，我们展示了十氢化萘如何以典型的FKBP51选择性结合构象锁定配体的关键选择性诱导环己基部分。最好的化合物29在HeLa衍生的KB细胞系中产生细胞死亡，Hela衍生的KB细胞系是宫颈腺癌的细胞模型，其中FKBP51高度表达。我们的结果表明，在保持FKBP51选择性的同时，如何可以使FKBP51抑制剂刚性化和扩展。此类抑制剂可能是治疗FKBP51失调的人类癌症的新型工具。