8-oxo-(E)-non-2-enoic acid methyl ester | 28979-90-0

• 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: 8-oxo-(E)-non-2-enoic acid methyl ester
• 英文别名: methyl 8-oxo-2-nonenate；Keto-8-nonen-2-carbonsaeure-methylester trans；methyl (2E)-8-oxo-2-nonenoate；methyl (E)-8-oxonon-2-enoate
• CAS: 28979-90-0
• 化学式: C₁₀H₁₆O₃
• 分子量: 184.235
• InChiKey: FKLLIAJRSNJJAA-SOFGYWHQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  13
• 可旋转键数：
  7
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  8-oxo-(E)-non-2-enoic acid methyl ester 在 nickel(II) salen 四丁基溴化铵 、 丙二酸二甲酯 作用下， 以 乙腈 为溶剂， 以70%的产率得到(2-hydroxy-2-methylcyclohexyl)acetic acid methyl ester
  参考文献：
  名称：

  催化还原镍（Salen）的间接电还原环化和电氢环化

  摘要：

  我们描述了为实现使用催化镍（II）salen作为介体的电还原环化（ERC）和电氢环化（EHC）反应所做的努力。虽然镍（II）沙仑被证明是有效的，但类似的钴配合物以及镍（II）环己酰胺均无效。使用汞池或环境上优选的网状玻璃碳（RVC）阴极，可实现60％至94％的收率转化。这些实施例代表了首先以这种方式使用镍salen配合物的情况。观察到ERC和EHC底物的伏安行为之间存在明显差异。二烯酸酯14例如显示出明显更大的催化电流。当结构修改后的介体31使用电子传输路径时会关闭。相反，还原形式的31表现为电生成的碱，导致分子内迈克尔加合物23的形成。据推测，修饰的配体的甲基降低了复合物的还原形式用作亲核试剂而不作为碱的能力。醛23还被表征为镍（II）salen介导的11的电还原环化的副产物。鉴于非介导过程中不存在它，因此其形成与介体的存在有关。为了说明结果，我们赞成存在一个机械连续体，该连续体涉及镍（

  DOI：

  10.1021/jo051148+
• 作为产物：
  描述：

  6-羟基己醛 在 4 A molecular sieve 、 pyridinium chlorochromate 作用下， 以 四氢呋喃 、 乙醚 、 乙腈 为溶剂， 反应 25.0h， 生成 8-oxo-(E)-non-2-enoic acid methyl ester
  参考文献：
  名称：

  在两种互补条件下通过串联分子内迈克尔-羟醛反应合成多环环丁烷衍生物：TBDMSOTf-Et3N 和 TMSI-(TMS)2NH

  摘要：

  通过串联的分子内迈克尔-羟醛反应序列，在 Et 3 N 存在下用 TBDMSOTf 或在 (TMS) 2 NH 存在下用 TMSI 处理在适当位置具有酮官能团的 α,β-不饱和酯，几种不同类型的环丁烷衍生物。这两种反应条件是互补的。三环[4.2.1.03-8]壬烷34和35、三环[5.1.1.0 3,8 ]壬烷40、三环[5.4.0.0 3,7 ]十一烷51、四环[5.4.0.0 3,7 .0 9,11 ]十一烷 45 和双环 [3.2.0] 庚烷 36、57 和 38，它们的结构部分或完全类似于端茚酸 A (1a)、B (1b) 和 C (2)、三羟基癸二烯(3)、lintenone (4)、italicene (3) 和 filifolone (6)，通过串联反应立体选择性地合成

  DOI：

  10.1021/ja00071a024

文献信息

• A novel rearrangement of cyclobutanes to cyclopropanes; construction of tricyclo[5.4.0.0]undecane and bicyclo[4.1.0]heptane systems
  作者：Masataka Ihara、Takahiko Taniguchi、Nobuaki Taniguchi、Keiichiro Fukumoto

  DOI：10.1039/c39930001477

  日期：——

  Treatment of hydroxylated cyclobutane derivatives with BF3·OEt2, POCl3 in the presence of pyridine or Raney nickel causes a novel rearrangement forming tricycle[5.4.0.0]undecane and bicyclo[4.1.0]heptane systems.

  在吡啶或阮内镍的存在下用BF 3 ·OEt 2，POCl 3处理羟基化的环丁烷衍生物会引起新的重排，形成三环[5.4.0.0]十一烷和双环[4.1.0]庚烷体系。
• Reductive Cyclization of Ketones Tethered to Activated Olefins Mediated by Magnesium in Methanol
  作者：Ge Hyeong Lee、Eun Bok Choi、Eun Lee、Chwang Siek Pak

  DOI：10.1021/jo00085a036

  日期：1994.3

  The reductive cyclizations of various ketones tethered to activated olefins such as alpha,beta-unsaturated esters, nitriles, sulfoxides, and sulfides were mediated by magnesium in dry methanol in the presence of mercuric chloride. When treated with magnesium in dry methanol at -23-degrees-C all of the ketones except nitrile 9 (42%) and 5-oxa-8-keto-2-enoate 5 (13%) gave excellent yields (79-98%) of mono- and bicyclic alcohol products resulting from carbon-carbon bond formation between the beta-carbon of the activated olefin and the carbonyl carbon. The reaction was accelerated by the catalytic amount of mercuric chloride, although the stereoselectivity was not affected by the catalyst. For all the substrates except 8-keto-2-enoate 3 and 5-aza-8-keto-2-enoate 6, the configuration of the major product was trans between the hydroxy and (methoxycarbonyl)methyl groups. The product isomer ratios were independent of the substrate geometry (E or Z). In contrast to the ketones, aldehydes tethered to alpha,beta-unsaturated esters gave products of simple reduction of the double bond and/or saturated alcohols instead of the cyclized products. When the reaction temperature was lowered, the yields of cyclized product were significantly affected by the production of appreciable amounts of saturated product, but the stereoselectivity was not improved. Under the same reaction conditions alpha,beta-unsaturated sulfoxide 16 gave deoxygenated sulfide 18 (85%) as the major product along with a small amount (9%) of cyclized product 19t. In contrast, sulfone 17 underwent desulfonylation instead of cyclization to give olefin 20 (54%). With excess magnesium (15 equiv), however, alpha,beta-unsaturated sulfoxide 16 gave cyclized sulfide 19t (95%) via deoxygenated sulfide 18. Both 16Z and 16E afforded product 19t as a single isomer. It is suggested that the reductive cyclization of the alpha,beta-unsaturated esters and nitriles proceed by means of nucleophilic attack of a beta-carbon radical anion, formed by initial electron transfer from magnesium metal to the activated olefin, on the carbonyl group. The cyclization of the alpha,beta-unsaturated sulfide proceeds by nucleophilic attack of the ketyl on the olefinic double bond.
• Intramolecular Michael addition of chiral imines to enoates: a new asymmetric carbocyclization reaction
  作者：Françoise Dumas、Jean d'Angelo

  DOI：10.1016/s0957-4166(00)82371-x

  日期：1990.1
• Miyaoka, Hiroaki; Nishiyama, Akira; Nagaoka, Hiroto, Synlett, 2003, # 5, p. 717 - 719
  作者：Miyaoka, Hiroaki、Nishiyama, Akira、Nagaoka, Hiroto、Yamada, Yasuji

  DOI：——

  日期：——
• Moreau,C. et al., Bulletin de la Societe Chimique de France, 1970, p. 545 - 549
  作者：Moreau,C. et al.

  DOI：——

  日期：——