2-Oxo-1-(3-oxopropyl)-1-cyclopentancarbonsaeure-ethylester | 6603-73-2

• 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-Oxo-1-(3-oxopropyl)-1-cyclopentancarbonsaeure-ethylester
• 英文别名: Ethyl 1-(2-formylethyl)-2-oxocyclopentanecarboxylate；2-Ethoxycarbonyl-2-(3-oxo-propyl)-cyclopentanon；Ethyl 2-oxo-1-(3-oxopropyl)cyclopentanecarboxylate；ethyl 2-oxo-1-(3-oxopropyl)cyclopentane-1-carboxylate
• CAS: 6603-73-2
• 化学式: C₁₁H₁₆O₄
• 分子量: 212.246
• InChiKey: IASBOYCSCKMQCG-UHFFFAOYSA-N

物化性质

• 沸点：
  319.8±27.0 °C(Predicted)
• 密度：
  1.122±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.5
• 重原子数：
  15
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  60.4
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  2-Oxo-1-(3-oxopropyl)-1-cyclopentancarbonsaeure-ethylester 在 sodium chlorite 、 sodium dihydrogenphosphate 、 2-甲基-2-丁烯 、 tetrakis(trifluoroacetato)rhodium(II) 、 三乙胺 、 氯甲酸异丁酯 作用下， 以 四氢呋喃 、 乙醚 、 二氯甲烷 、 叔丁醇 为溶剂， 反应 6.5h， 生成
  参考文献：
  名称：

  α-重氮-β-羟基酮的重排以合成双环[ m]。n .1]烷酮

  摘要：

  铑催化的稠合双环α-重氮-β-羟基酮的分解可产生桥联双环[ m]的良好收率。n .1]酮通过重排途径。

  DOI：

  10.1021/acs.orglett.7b01963
• 作为产物：
  描述：

  2-氧代环戊羧酸乙酯 、 丙烯醛 在 potassium carbonate 作用下， 以 甲苯 为溶剂， 反应 1.5h， 以75%的产率得到2-Oxo-1-(3-oxopropyl)-1-cyclopentancarbonsaeure-ethylester
  参考文献：
  名称：

  α-重氮-β-羟基酮的重排以合成双环[ m]。n .1]烷酮

  摘要：

  铑催化的稠合双环α-重氮-β-羟基酮的分解可产生桥联双环[ m]的良好收率。n .1]酮通过重排途径。

  DOI：

  10.1021/acs.orglett.7b01963

文献信息

• Ytterbium triflate catalyzed Michael additions of β-ketoesters in water
  作者：Erik Keller、Ben L. Feringa

  DOI：10.1016/0040-4039(96)00141-4

  日期：1996.3

  Michael addition of various β-ketoesters towards enones and α,β-unsaturated aldehydes resulted in a quantitative conversion to the corresponding 1,4-adducts by performing the reactions in water in the presence of ytterbium triflate as a water-tolerant Lewis acid.

  在三氟甲磺酸y作为耐水的路易斯酸存在下，通过在水中进行反应，将各种β-酮酸酯迈克尔加成成烯酮和α，β-不饱和醛导致定量转化为相应的1,4-加合物。
• SmI₂/Pd(0)-Mediated Intramolecular Coupling between Propargylic Esters and Tethered Aldehydes or Ketones
  作者：José M. Aurrecoechea、Roberto Fañanás、Mónica Arrate、José M. Gorgojo、Natalia Aurrekoetxea

  DOI：10.1021/jo9819133

  日期：1999.3.1

  chelating trivalent samarium and facilitating retroaldol-aldol-type equilibria in the product. In this latter case, the strategic combination of chemoselective carbonyl addition and SmI(2)/Pd(0)-promoted cyclization provides ready and convenient stereocontrolled access to functionalized cyclopentanols from unprotected 1,5-dicarbonyl starting materials. The analogous formation of cyclohexanols is limited by

  描述了炔丙基酯和羰基化合物之间的SmI（2）/ Pd（0）促进的分子内偶联。反应得到高炔丙基环烷醇产物。当使用酮作为羰基组分时，环戊醇以高收率形成，但是发现醛在这些反应中不是合适的伙伴。与相邻的功能化四元中心有效地形成产物特别引人注目。这些环化反应在新生成的炔丙基和甲醇立体异构中心附近具有低非对映选择性，除非这两个中心是季铵盐或存在能够螯合三价sa并促进产物中逆醛醇-醛醇型平衡的基团。在后一种情况下，化学选择性羰基加成和SmI（2）/ Pd（0）促进的环化的战略组合，提供了从不受保护的1,5-二羰基起始原料中轻松便捷地立体控制官能化环戊醇的方法。环己醇的类似形成受到环化产率低和缺乏立体选择性的限制。
• Non-Biaryl Atropisomers in Organocatalysis
  作者：Sebastian Brandes、Barbara Niess、Marco Bella、Auxiliadora Prieto、Jacob Overgaard、Karl Anker Jørgensen

  DOI：10.1002/chem.200600495

  日期：2006.8.7

  ketone, in up to 93 % ee (ee=enantiomeric excess), as well as for the asymmetric Friedel-Crafts amination of a variety of 2-naphthols, permitting the preparation of the latter in up to 98 % ee. The aminated 8-amino-2-naphthol itself is the first chiral organocatalyst based on non-biaryl atropisomerism. The two enantiomers of this chiral primary amine can be used for the direct alpha-fluorination of alpha-branched

  可以通过简单的胺化步骤制备一种新的6'-羟基金鸡纳生物碱，该类生物碱在喹啉核心的5'位置具有非联芳基阻转异构功能。这些是金鸡纳生物碱经典核心中引入的阻转异构原理的第一批衍生物。胺化的金鸡纳生物碱是有效的有机催化剂，可将高达93％ee（ee =对映体过量）的β-酮酸酯迈克尔加成到丙烯醛和甲基乙烯基酮中，以及各种不对称的Friedel-Crafts胺化反应。 2-萘酚，允许制备高达98％ee的后者。胺化的8-氨基-2-萘酚本身是第一种基于非联芳基阻转异构的手性有机催化剂。该手性伯胺的两种对映异构体可用于α-支化醛的直接α-氟化。氟化化合物因此可以以高达90％ee的浓度进入。
• Electroorganic Chemistry. 144. Electroreductive Coupling of Ketones with O-Methyl Oximes, N,N-Dimethylhydrazones, and Nitrones. A Convenient Route to Synthesis of .beta.-Amino Alcohol
  作者：Tatsuya Shono、Naoki Kise、Taku Fujimoto、Ayuko Yamanami、Ryoji Nomura

  DOI：10.1021/jo00086a023

  日期：1994.4

  The intermolecular coupling of a variety of ketones with some types of O-methyl oximes took place when a mixture of both components was electrochemically reduced in i-PrOH with an Sn cathode. The product, beta-methoxyamino alcohol was easily converted to beta-amino alcohol by simple reduction. A chiral ligand effective for the enantioselective addition of diethylzinc to an aldehyde was easily obtained from the product formed by the electroreductive coupling of (-)-menthone with O-methylacetaldoxime. The intermolecular coupling of a ketone with a N,N-dimethylhydrazone or nitrone was also promoted by the electroreduction. Furthermore, the electroreductive coupling of a carbonyl group with an intramolecular O-methyl oxime moiety gave the corresponding cyclized product stereoselectively.
• 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.