methyl Z-7-oxooct-2-enoate | 113704-93-1

• 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: methyl Z-7-oxooct-2-enoate
• 英文别名: methyl (Z)-7-oxooct-2-enoate
• CAS: 113704-93-1
• 化学式: C₉H₁₄O₃
• 分子量: 170.208
• InChiKey: CZDIAFWZQBFKHZ-ALCCZGGFSA-N

物化性质

• 沸点：
  267.9±33.0 °C(Predicted)
• 密度：
  0.993±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.47
• 重原子数：
  12.0
• 可旋转键数：
  5.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.56
• 拓扑面积：
  43.37
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  methyl Z-7-oxooct-2-enoate 在 sodium tetrahydroborate 、 水 、 sodium hydride 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 反应 1.25h， 生成 (2S,6S)-(6-methyltetrahydropyran-2-yl)acetic acid
  参考文献：
  名称：

  Michael addition of N- and O-centred nucleophiles to tethered acrylates. The role of double bond geometry in controlling the diastereoselectivity of cyclisations leading to 2,6-disubstituted tetrahydropyrans and piperidines

  摘要：

  底物 1-4 很容易发生环化，得到相应的 2,6-二取代四氢吡喃或哌啶。底物内迈克尔受体的碳-碳双键的几何形状对环化过程的非对映选择性有显着影响。

  DOI：

  10.1039/p19960000967
• 作为产物：
  描述：

  1-甲基环戊烯 在 18-冠醚-6 、 臭氧 、 三苯基膦 、 乙腈 作用下， 以 二氯甲烷 、 甲苯 为溶剂， 反应 0.5h， 生成 methyl Z-7-oxooct-2-enoate
  参考文献：
  名称：

  Intramolecular Michael Addition of N- and O-Centred Nucleophiles to Tethered Acrylates. The Role of Double-Bond Geometry in Controlling the Diastereo- selectivity of Cyclizations Leading to 2,6-Disubstituted Tetrahydropyrans and Piperidines.

  摘要：

  羟基丙烯酸酯 E-(5)的氧阴离子 发生顺畅的分子内迈克尔加成反应，得到反式-2,6-二取代的四氢吡喃（7 反式-2,6-二取代的四氢吡喃（7）作为主要反应产物。 反应的主要产物。相反，从异构体 Z-(5) 环化生成 顺式-2,6-二取代的四氢吡喃（6）为主要反应产物。 产品。这种化学反应已经扩展到对映体选择性合成 (+)-(6) 的对映体选择性合成。 酸 (+)-(2) 的正式全合成。 (Viverra civetta)腺分泌物的一种成分。酮基丙烯酸酯的还原胺化反应 (12) 发生还原胺化反应，生成中间胺，并在原位环化、 在原位环化，生成 顺式-2,6-二取代哌啶 (26)。类似的 处理化合物 (13) 得到异构体 反式-2,6-二取代哌啶（27）作为唯一的 反应产物。有人提出了过渡态结构来解释 在所有环化反应中观察到的非对映选择性。

  DOI：

  10.1071/c97173

文献信息

• Intramolecular 1,3-dipolar cycloadditions of dihydroimidazolium ylides: synthesis of pyrrolo[1,2,3-de]quinoxalines and imidazo[1,2-a]indoles
  作者：Pedro M. J. Lory、Raymond C. F. Jones、James N. Iley、Simon J. Coles、Michael B. Hursthouse

  DOI：10.1039/b605458g

  日期：——

  an intramolecular 1,3-dipolar cycloaddition reaction that affords (via a reaction cascade involving eliminative ring-opening, recyclisation and prototropic tautomerism) unexpected hexahydropyrrolo[1,2,3-de]quinoxaline products. Steric bulk in both the dihydroimidazole and the dipolarophile allows isolation of an imidazo[1,2-a]indole, the initial product of cycloaddition. When the bromomethyl ketone

  用含烯烃的溴甲基酮进行4,5-二氢咪唑的N-烷基化反应以及用DBU处理如此形成的4,5-二氢咪唑鎓离子会引起分子内1,3-偶极环加成反应（通过涉及反应的级联反应）消除开环，环化和质子互变异构）意外的六氢吡咯并[1,2,3-de]喹喔啉产品。在二氢咪唑和亲二氟体中的立体异构体都可以分离出咪唑并[1,2-a]吲哚，这是环加成反应的初始产物。当溴甲基酮不包含其他官能团时，或者由于空间限制而抑制环加成时，二氢咪唑鎓离子会进行开环水解，然后对暴露的氨基酮进行环化，从而获得3-烷基-1-甲酰基哌嗪-2-酮或3-芳基-1-甲酰基-1,4,5，
• Pyrrolo[1,2,3-de]quinoxalines: unexpected products from 1,3-dipolar cycloaddition of dihydroimidazolium ylides
  作者：Raymond C.F Jones、James N Iley、Pedro M.J Lory、Simon C Coles、Mark E Light、Michael B Hursthouse

  DOI：10.1016/s0040-4039(01)00617-7

  日期：2001.6

  4,5-Dihydroimidazoles undergo an N-alkylation and 1,3-dipolar cycloaddition cascade with unsaturated α-bromoketones, with subsequent eliminative ring-opening, recyclisation and tautomerisation to form unexpected hexahydropyrrolo[1,2,3-de]quinoxalines.

  4,5-二氢咪唑与不饱和α-溴酮进行N-烷基化和1,3-偶极环加成反应，随后消除开环，环化和互变异构现象，形成意外的六氢吡咯并[1,2,3- de ]喹喔啉。
• Michael addition of N- and O-centred nucleophiles to tethered acrylates. The role of double bond geometry in controlling the diastereoselectivity of cyclisations leading to 2,6-disubstituted tetrahydropyrans and piperidines
  作者：Martin G. Banwell、Chinh T. Bui、Ha T. T. Pham、Gregory W. Simpson

  DOI：10.1039/p19960000967

  日期：——

  Cyclisation of substrates 1–4 occurs readily to give the corresponding 2,6-disubstituted tetrahydropyran or piperidine. The geometry about the carbon–carbon double bond of the Michael acceptor within the substrate is shown to have a significant impact on the diastereoselectivity of the cyclisation process.

  底物 1-4 很容易发生环化，得到相应的 2,6-二取代四氢吡喃或哌啶。底物内迈克尔受体的碳-碳双键的几何形状对环化过程的非对映选择性有显着影响。
• 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.
• Electroreductive cyclization. Ketones and aldehydes tethered to .alpha.,.beta.-unsaturated esters (nitriles). Fundamental investigations
  作者：R. Daniel Little、Dennis P. Fox、Luc Van Hijfte、Robert Dannecker、Gregory Sowell、Ronald L. Wolin、Luc Moens、Manuel M. Baizer

  DOI：10.1021/jo00245a029

  日期：1988.5