2-<5-(1-carbomethoxypent-2-enyl)>cyclohexanone | 96293-26-4

• 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: 2-<5-(1-carbomethoxypent-2-enyl)>cyclohexanone
• 英文别名: Methyl trans-5-(2'-oxocyclohexyl)-2-pentenoate；5-<2-Oxo-cyclohexyl>-pent-2t-ensaeure-methylester；methyl (E)-5-(2-oxocyclohexyl)pent-2-enoate
• CAS: 96293-26-4
• 化学式: C₁₂H₁₈O₃
• 分子量: 210.273
• InChiKey: FGUOUYUAAAKNPS-WEVVVXLNSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.26
• 重原子数：
  15.0
• 可旋转键数：
  4.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.67
• 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：

  2-<5-(1-carbomethoxypent-2-enyl)>cyclohexanone 以73%的产率得到
  参考文献：
  名称：

  ENHOLM, ERIC J.;TRIVELLAS, ANTIGONE, TETRAHEDRON LETT., 30,(1989) N, C. 1063-1066

  摘要：

  DOI：
• 作为产物：
  描述：

  1.3-丁二烯酸甲酯 、 Cyclohexanone-2-carbaldehyde 以 二甲基亚砜 为溶剂， 生成 2-<5-(1-carbomethoxypent-2-enyl)>cyclohexanone
  参考文献：
  名称：

  β-乙烯基丙烯酸甲酯与甲酰基环烷酮的反应。：功能化螺化合物的新途径。

  摘要：

  DOI：

  10.1016/s0040-4039(01)88688-3

文献信息

• X=Y-ZH Systems as potential 1,3-dipoles
  作者：Harriet Ardill、Ronald Grigg、Visuvanathar Sridharan、Sivagnanasundram Surendrakumar

  DOI：10.1016/s0040-4020(01)86199-8

  日期：1988.1

  decarboxylation, followed by intramolecular cycloaddtion of the resultant non-stabilised azomethine ylides. Evidence is produced for syn-anti dipole equilibration and it is found that intramolecular cycloadditions to a terminal alkyne involve only the anti-dipole and proceed via an exotransition state to give a single cycloadduct. In contrast, intramolecular cycloaddition to a terminal alkene involves

  将一系列无环和环状仲α-氨基酸与含有最接近的末端烯烃或炔烃的芳基醛一起加热，会导致连续的缩合和脱羧，然后将所得的非稳定的甲亚甲酰亚胺分子内环加成。产生了顺-反偶极平衡的证据，并且发现分子内环加成至末端炔烃仅涉及反偶极并通过外过渡态进行以给出单个环加合物。相反，分子内环加成至末端烯烃涉及反偶极和顺偶极，在能量上优选俘获前者，导致两种立体异构体环加合物的混合物。
• Tandem intramolecular Michael addition and 1,3-dipolar cycloaddition reactions of oximes; versatile new carbon–carbon bond forming methodology
  作者：Paul Armstrong、Ronald Grigg、Sivagnanasundram Surendrakumar、William J. Warnock

  DOI：10.1039/c39870001327

  日期：——

  Oximes undergo intramolecular Michael addition to proximate electronegative alkenes, generating cyclic nitrones which can be trapped inter- and intra-molecularly in 1,3-dipolar cycloaddition reactions taking place either separately or in tandem.

  肟经过分子内迈克尔加成反应，形成邻近的负电性烯烃，生成环状硝酮，可被分子间和分子内捕获在分别或串联发生的1,3-偶极环加成反应中。
• 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.
• X = Y - ZH systems as potential 1,3-dipoles part 35. Generation of nitrones from oximes. Class 3 processes. Tandem intramolecular michael addition (1,3-azaprotio cyclotransfer) - intermolecular 1,3-dipolar cycloaddition reactions.
  作者：Ronald Grigg、Jasothara Markandu、Trevor Perrior、Sivagnanasundram Surendrakumar、William J. Warnock

  DOI：10.1016/s0040-4020(01)89883-5

  日期：1992.1

  Aldoximes and ketoximes possessing gamma- or delta-alkenyl substituents undergo thermal conversion to 5- and 6- membered cyclic nitrones via a 1,3-azaprotio cyclotransfer, a 2n + 2-sigma + 2-pi concerted process, rather than a Michael addition. The reactions can be performed as a tandem nitrone formation-cycloaddition sequence or, if required, the intermediate nitrones can be isolated. The cycloadditions usually proceed via an exo-transition state and show both regio- and diastereofacial-specificity. Preliminary attempts at chiral induction via a menthyl auxiliary are reported.
• 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