E-2,2,5-trimethylhexa-3,5-dienal | 80868-27-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: E-2,2,5-trimethylhexa-3,5-dienal
• 英文别名: (3E)-2,2,5-trimethylhexa-3,5-dienal
• CAS: 80868-27-5
• 化学式: C₉H₁₄O
• 分子量: 138.21
• InChiKey: KCQBRFGQEVUNON-AATRIKPKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  10
• 可旋转键数：
  3
• 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：

  E-2,2,5-trimethylhexa-3,5-dienal 在 六甲基磷酰三胺 、 potassium fluoride 、 lithium 、 乙胺 、 叔丁醇 作用下， 以 四氢呋喃 、 甲醇 、 乙醚 、 苯 为溶剂， 反应 21.25h， 生成 (4aR^*,9aS^*)-4,4a,5,6,7,8,9,9a-octahydro-2,9,9-trimethyl-3H-benzocyclohepten-5-ol
  参考文献：
  名称：

  A Convergent Synthesis of (�)-?- and ?-Himachalenes

  摘要：

  Abstract(±)‐α and β‐Himachalene, 5 and 6, have been synthesized in a convergent manner from 3,3‐dimethylacrolein (9), the ester enolate 10 and the silyloxypentadienyllithium 7. The key steps are the regioselective γ‐addition of the dienal 13 to 7 and the intramolecular Diels‐Alder addition 15 → 16. Hydrogenolysis of the diethylphosphate group and functionalization at C (5) completed the synthesis of 5 and 6.

  DOI：

  10.1002/hlca.19810640815
• 作为产物：
  描述：

  ethyl (E)-2,2,5-trimethyl-3,5-hexadienoate 在 lithium aluminium tetrahydride 、 pyridinium chlorochromate 作用下， 以 乙醚 、 二氯甲烷 为溶剂， 反应 4.5h， 生成 E-2,2,5-trimethylhexa-3,5-dienal
  参考文献：
  名称：

  A Convergent Synthesis of (�)-?- and ?-Himachalenes

  摘要：

  Abstract(±)‐α and β‐Himachalene, 5 and 6, have been synthesized in a convergent manner from 3,3‐dimethylacrolein (9), the ester enolate 10 and the silyloxypentadienyllithium 7. The key steps are the regioselective γ‐addition of the dienal 13 to 7 and the intramolecular Diels‐Alder addition 15 → 16. Hydrogenolysis of the diethylphosphate group and functionalization at C (5) completed the synthesis of 5 and 6.

  DOI：

  10.1002/hlca.19810640815

文献信息

• Selective Demetalations of Iron Diene Complexes. Expedient Synthesis of Substituted (<i>Z</i>)-Allylalcohols
  作者：Jutta Böhmer、Walter Förtsch、Rainer Schobert

  DOI：10.1055/s-1997-1537

  日期：1997.9

  (3E)-6-Oxo-1,3-dienetricarbonyliron complexes 1 can be demetalated in good yields exclusively either to the free unrearranged (3E)-6-oxodiene 2 with ceric ammonium nitrate in methanol or to the (2Z)-6-oxoallylalcohol 3 by an excess of NaOH/H2O2.

  (3E)-6-氧代-1,3-二烯三羰基铁配合物1可以在良好收率下，通过硫酸铈铵在甲醇中脱金属化，专一性地得到未重排的(3E)-6-氧代二烯2，或者通过过量的氢氧化钠/过氧化氢脱金属化得到(2Z)-6-氧代烯丙醇3。
• Regioselective Synthesis of Substituted (3E)-1,3-Dienes from Chelated Allyl-Ironcarbene Complexes and Potassium Enoxyborates
  作者：Jutta Böhmer、Frank Hampel、Rainer Schobert

  DOI：10.1055/s-1997-1394

  日期：1997.6

  The addition of potassium enoxyborates to the chelated allyl-iron-carbene complex 1 leads to the corresponding η 4-(3E)-1,3-diene complexes 2 in fair yields. Complexes 2 can be demetalated with ceric ammonium nitrate (CAN) to give unrearranged (3E)-t-oxo-1,3-dienes 3. Prior to decomplexation, the carbonyl group can be further modified. This is demonstrated by the syntheses of the natural terpene alcohol hotrienol and of a complexed methylene-separated dienyne. Potassium enoxyborates are superior to lithium enolates as they are readily prepared in situ from a variety of aldehydes and ketones which do not form sufficiently stable lithium derivatives. In contrast to lithium enolates, only C-C coupling products derived from the "kinetic" regioisomers are formed from unsymmetrical aliphatic ketones.

  将钾酯硼酸盐添加到螯合的烯丙基铁碳烯复合物1中，可以在合理产率下得到相应的 η 4-(3E)-1,3-二烯复合物2。复合物2可以用铈铵硝酸盐（CAN）去金属化，得到未重新排列的 (3E)-t-氧基-1,3-二烯3。在去复合之前，可以进一步修饰羰基。这通过合成天然萜醇霍特里诺尔和一种复合的亚甲基分隔的二炔来证明。钾酯硼酸盐优于锂烯醇盐，因为它们可以在多种不形成足够稳定的锂衍生物的醛和酮中原位制备。与锂烯醇盐相比，仅从不对称脂肪族酮中形成源自“动能”区域异构体的C-C偶联产物。
• LIC-KOR-PROMOTED ACCESS TO A TETRAHYDROINDANONE PRECURSOR
  作者：Paolo Balma Tivola、Annamaria Deagostino、Cristina Prandi、Paolo Venturello

  DOI：10.1081/scc-100103333

  日期：2001.1

  The trans-fused tetrahydroindanone ring system 6 can be synthesized by intramolecular Diels-Alder cycloaddition of activated triene 5. The preparation of this intermediate is readily promoted by the LIC-KOR-promoted metalation of crotonaldehyde dimethyl acetal.
• A Convergent Synthesis of (�)-?- and ?-Himachalenes
  作者：Wolfgang Oppolzer、Roger L. Snowden

  DOI：10.1002/hlca.19810640815

  日期：1981.12.16

  Abstract(±)‐α and β‐Himachalene, 5 and 6, have been synthesized in a convergent manner from 3,3‐dimethylacrolein (9), the ester enolate 10 and the silyloxypentadienyllithium 7. The key steps are the regioselective γ‐addition of the dienal 13 to 7 and the intramolecular Diels‐Alder addition 15 → 16. Hydrogenolysis of the diethylphosphate group and functionalization at C (5) completed the synthesis of 5 and 6.