(2E,6E)-methyl 7-nitro-2,6-octadienoate | 124126-07-4

• 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: (2E,6E)-methyl 7-nitro-2,6-octadienoate
• 英文别名: methyl (2E,6E)-7-nitro-2,6-octadienoate；methyl (E,E)-7-nitro-2,6-octadienoate；methyl (2E,6E)-7-nitroocta-2,6-dienoate
• CAS: 124126-07-4
• 化学式: C₉H₁₃NO₄
• 分子量: 199.207
• InChiKey: UUDDOJUFDIJAEO-KQQUZDAGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  14
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.44
• 拓扑面积：
  72.1
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (2E,6E)-methyl 7-nitro-2,6-octadienoate 在 三甲基铝 、 碳酸氢钠 作用下， 以 二氯甲烷 、 甲苯 为溶剂， 反应 6.0h， 生成
  参考文献：
  名称：

  A Systematic Investigation of Quaternary Ammonium Ions as Asymmetric Phase-Transfer Catalysts. Synthesis of Catalyst Libraries and Evaluation of Catalyst Activity

  摘要：

  Despite over three decades of research into asymmetric phase-transfer catalysis (APTC), a fundamental understanding of the factors that affect the rate and stereoselectivity of this important process are still obscure. This paper describes the initial stages of a long-term program aimed at elucidating the physical organic foundations of APTC employing a chemoinformatic analysis of the alkylation of a protected glycine imine with libraries of enantiomerically enriched quaternary ammonium ions. The synthesis of the quaternary ammonium ions follows a diversity:oriented approach wherein the tandem inter [4 + 2]/intra[3 + 2] cycloaddition of nitroalkenes serves as the key transformation. A two-part synthetic strategy comprised of (1) preparation of enantioenriched scaffolds and (2) development of parallel synthesis procedures is described. The strategy allows for the facile introduction of four variable groups in the vicinity of a stereogenic quaternary ammonium ion. The quaternary ammonium ions exhibited a wide range of activity and to a lesser degree enantioselectivity. Catalyst activity and selectivity are rationalized in a qualitative way on the basis of the effective positive potential of the ammonium ion.

  DOI：

  10.1021/jo2005445
• 作为产物：
  描述：

  (E)-methyl-6-hydroxy-hex-2-en-oate 在 potassium tert-butylate 、 三乙胺 、 pyridinium chlorochromate 、 三氟乙酸酐 作用下， 生成 (2E,6E)-methyl 7-nitro-2,6-octadienoate
  参考文献：
  名称：

  串联[4 + 2] / [3 + 2]-环加成。2.手性乙烯基醚的不对称诱导

  摘要：

  乙烯基醚可有效引发串联连接到α，β-不饱和酯双极性亲和剂的硝基烯烃的串联[4 + 2] / [3 + 2]-环加成反应。使用手性乙烯基醚6作为亲二烯体，硝基烯烃1和2经历高度选择性的串联环加成。所得到的亚硝基缩醛的氢解裂解产生了> 98％ee的α-羟基内酰胺（-）- 14和（-）- 21，手性助剂的回收率很高。可以看出，非对映异构体的高选择性源于对乙烯基醚的强烈内在偏爱以及助剂中固有的表面偏向。

  DOI：

  10.1016/s0040-4020(01)85599-x

文献信息

• Tandem [4+2]/[3+2]-cycloadditions. 2. Asymmetric induction with a chiral vinyl ether
  作者：Scott E. Denmark、C.B.W. Senanayake、Ho Ginny-Dai

  DOI：10.1016/s0040-4020(01)85599-x

  日期：1990.1

  A tandem [4+2]/[3+2]-cycloaddition of nitroalkenes tethered to α,β-unsaturated ester dipolarophiles can be effectively triggered with a vinyl ether. Using the chiral vinyl ether 6 as the dienophile, nitroalkenes 1 and 2 undergo highly selective tandem cycloaddition. Hydrogenolytic cleavage of the resulting nitroso acetals produce α-hydroxy lactams (-)-14 and (-)-21 in >98% e.e. with excellent recovery

  乙烯基醚可有效引发串联连接到α，β-不饱和酯双极性亲和剂的硝基烯烃的串联[4 + 2] / [3 + 2]-环加成反应。使用手性乙烯基醚6作为亲二烯体，硝基烯烃1和2经历高度选择性的串联环加成。所得到的亚硝基缩醛的氢解裂解产生了> 98％ee的α-羟基内酰胺（-）- 14和（-）- 21，手性助剂的回收率很高。可以看出，非对映异构体的高选择性源于对乙烯基醚的强烈内在偏爱以及助剂中固有的表面偏向。
• Tandem [4 + 2]/[3 + 2] cycloadditions: facile and stereoselective construction of polycyclic frameworks
  作者：Scott E. Denmark、Young Choon Moon、C. B. W. Senanayake

  DOI：10.1021/ja00157a048

  日期：1990.1

  We describe herein a simple strategy, which expands the utility of the nitronates by intramolecularly coupling a 1,3-dipolar cycloaddition with the [4+2] process that creates them

  我们在此描述了一个简单的策略，它通过将 1,3-偶极环加成与产生它们的 [4+2] 过程进行分子内偶联来扩展硝基的效用
• [2+3] CycloadditionsBetween Nitroalkenes and Camphor-Derived Oxazoline<i>N</i>-Oxidesand Radical Denitration of the Adducts
  作者：Cyrille Kouklovsky、Yves Langlois、Arnaud Voituriez、Julien Moulinas

  DOI：10.1055/s-2003-40191

  日期：——

  [2+3] Cycloadditions between camphor-derived oxazoline N-oxide 2 and nitroalkenes 3a-f afforded stereoselectively adducts 4a-f. Radical denitration followed by acidic hydrolysis gave rise to anti-aldols 8a,b. The radical intermediate was also trapped by a suitable alkene, giving rise to a single stereoisomer.

  樟脑衍生的噁唑啉 N-氧化物 2 与硝基烯 3a-f 发生[2+3] 环加成反应，生成立体选择性加合物 4a-f。自由基脱氮后进行酸性水解，可得到反醛 8a,b。自由基中间体也会被合适的烯烃捕获，从而产生单一的立体异构体。
• Tandem inter [4+2]/intra [3+2] nitroalkene cycloadditions. 4. Cycloadditions with (E)- and (Z)-1-propenyl ethers
  作者：Scott E. Denmark、C. B. W. Senanayake

  DOI：10.1021/jo00059a043

  日期：1993.3

  The tandem [4 + 2]/[3 + 2] cycloaddition of nitroalkene 1 was initiated efficiently by 1-propenyl ethers as the dienophile. Ethyl(E)-1-propenyl ether reacted highly selectively to give a single nitro so acetal cycloadduct 6. Hydrogenolysis of 6 afforded a single isomer of alpha-hydroxy lactam 8 wherein the newly installed methyl group occupied the beta-configuration. Similarly, ethyl(Z)-1-propenyl ether produced an anomeric mixture of cycloadducts 7a and 7b which afforded a single alpha-hydroxy lactam 9 upon hydrogenolysis. The methyl group in 9 occupied the alpha-orientation. The high and complementary selectivity for production of 8 and 9 was explained on the basis of an extreme endo preference for the ethoxy group of the 1-propenyl ether in the [4 + 2] cycloaddition.
• Tandem inter [4+2]/intra [3+2]nitroalkene cycloadditions. 5. Origin of the Lewis acid dependent reversal of stereoselectivity
  作者：Scott E. Denmark、Mark E. Schnute、C. B. W. Senanayake

  DOI：10.1021/jo00059a044

  日期：1993.3

  The stereochemical course of the tandem [4 + 2]/[3 + 2] nitroalkene cycloaddition with chiral enol ethers has been shown to exhibit remarkable sensitivity to the nature of the Lewis acid promoter. Cycloadditions using (+)-camphor-derived vinyl ether 3 or (-)-trans-2-phenylcyclohexanol-derived vinyl ether 6 gave a predominance of the 1S hydroxy lactam 4 when promoted by Ti(O-i-Pr)2Cl2. The same vinyl ethers selectively produced the 1R hydroxy lactam 4 when promoted by MAPh. The (E)- and (Z)-1-propenyl ethers of (-)-trans-2-phenylcyclohexanol have been used to investigate the reversal of selectivity. Cycloadditions promoted by Ti(O-i-Pr)2Cl2 were found to be endo selective (12:1), while MAD and MAPh favored exo approach of the dienophile. High levels of asymmetric induction were observed in the endo mode of the cycloaddition for propenyl ethers (E)-13 and (Z)-13, 97.9% ee and 82.2% ee, respectively, but an erosion of selectivity occurred in the exo mode (72.2% ee) presumably through an s-cis enol ether conformation.