2-(methoxycarbonyl)-2-cyclopenten-1-one

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: 2-(methoxycarbonyl)-2-cyclopenten-1-one
• 英文别名: tert-butyl 5-oxocyclopent-1-ene-1-carboxylate；2-tert-butoxycarbonyl-2-cyclopenten-1-one；Tert-butyl 5-oxocyclopentene-1-carboxylate
• 化学式: C₁₀H₁₄O₃
• 分子量: 182.219
• InChiKey: AQXPKLCFLSIDER-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  13
• 可旋转键数：
  3
• 环数：
  1.0
• 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：

  2-(methoxycarbonyl)-2-cyclopenten-1-one 在 sodium tetrahydroborate 、 RuCl2(κ4-N,N'-bis[o-(diphenylphosphino)benzylidene]-(1S,2S)-diiminocyclohexane) 、 triethyloxonium hexaflourophosphate 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 生成 tert-butyl (8R,13S,14S,17S)-17-hydroxy-3-methoxy-6,7,8,12,14,15,16,17-octahydro-13H-cyclopenta[a]phenanthrene-13-carboxylate
  参考文献：
  名称：

  Enantioselective Diels-Alder Reactions of Unsaturated ?-Ketoesters Catalyzed by Chiral Ruthenium PNNP Complexes

  摘要：

  We report here dicationic ruthenium PNNP complexes that promote the enantioselective Diels-Alder reaction of alpha-methylene beta-ketoesters with various dienes. Complex [Ru(OEt(2))(2)(PNNP)](PF(6))(2), formed in situ from [RuCl(2)(PNNP)] and (Et(3)O)PF(6)(2 equiv.), catalyzes the Diels-Alder reaction of such unsaturated beta-ketoesters to give novel alkoxycarbonyltetrahydro-1-indanone derivatives (nine examples) with up to 93% ee. The crystal structure of the substrate-catalyst adduct shows that the lower face of the substrate is shielded by a phenyl ring of the PNNP ligand, which accounts for the high enantioselectivity. The attack of the diene from the open re enantioface of the unsaturated beta-ketoester is consistent with the absolute configuration of the product. A useful application of this method is the reaction with Dane's diene to give estrone derivatives with up to 99% ee and an ester-exo:endo ratio of up to 145:1 (after recrystallization). Besides the enantioselective formation of all-carbon quaternary centers, this methodology is notable because unsaturated beta-ketoesters have been rarely used in Diels-Alder reactions. Furthermore, enantiomerically pure estrone derivatives are interesting in view of their potential applications, including the treatment of breast cancer.

  DOI：

  10.2533/chimia.2011.231

文献信息

• Enantioselective Ficini Reaction: Ruthenium/PNNP-Catalyzed [2+2] Cycloaddition of Ynamides with Cyclic Enones
  作者：Christoph Schotes、Antonio Mezzetti

  DOI：10.1002/anie.201007753

  日期：2011.3.21

  Chiral cyclobuteneamides made easy: Double chloride abstraction from the ruthenium/PNNP complex 1 in the presence of unsaturated β‐keto esters 2 gives the dicationic adducts [Ru(2)(PNNP)]2+ (3) that catalyze the [2+2] cycloaddition of a variety of ynamides 4 to produce cyclobuteneamides 5 with high yield and enantioselectivity (see scheme).

  手性环丁烯酰胺很容易：在不饱和β-酮酸酯2存在下从钌/ PNNP配合物1中提取双氯化物，得到了催化[2 + 2 ]的二价加合物[Ru（2）（PNNP）] 2+（3）。各种ynamides的]环4，以产生cyclobuteneamides 5以高收率和对映选择性（参见方案）。
• Bicyclo[3.2.0]heptane-Based Enamides by Ru/PNNP-Catalyzed Enantioselective Ficini Reactions: Scope and Application in Ligand Design
  作者：Antonio Mezzetti、Christoph Schotes、Raphael Bigler

  DOI：10.1055/s-0031-1289679

  日期：2012.2

  converted into highly modular diene, phosphite-alkene, and diphosphite derivatives, which were tested as bidentate ligands with Rh(I), Ir(I), and Pd(II). asymmetric catalysis - biaryls - cycloaddition - bicyclic compounds - ligands - phosphorus - ruthenium

  从[RuCl 2（PNNP）]中提取双氯化物[PNNP =（S，S）-N，N'-双[ o-（二苯基膦基）亚苄基]环己烷-1,2-二胺]给出了难以确定的双阳离子加合物[Ru（ OEt）2（PNNP）] 2+催化环状亚烷基β-酮酯与各种炔酰胺的[2 + 2]环加成反应，从而以高收率和对映选择性生产基于双环[3.2.0]庚烷的酰胺。讨论了这些产品的结构特征，并将选定的实例转换为高度模块化的二烯，亚磷酸酯-烯烃和二亚磷酸酯衍生物，将其作为Rh（I），Ir（I）和Pd（II）的双齿配体进行了测试。 不对称催化-联芳基-环加成-双环化合物-配体-磷-钌
• Synthesis and Antitumor Activities of Novel 6-5 Fused Ring Heterocycle Antifolates: N-[4-[.omega.-(2-Amino-4-substituted-6,7-dihydrocyclopenta[d]pyrimidin-5-yl)alkyl]benzoyl]-L-glutamic Acids
  作者：Yoshihiko Kotake、Atsumi Iijima、Kentaro Yoshimatsu、Naoko Tamai、Yoichi Ozawa、Nozomu Koyanagi、Kyosuke Kitoh、Hiroaki Nomura

  DOI：10.1021/jm00037a012

  日期：1994.5

  molecule. The synthetic method involves (1) synthesis of key intermediates of tert-butyl 4-[omega-(2-substituted-3-oxocyclopentanyl) alkyl]benzoates (8a,b and 9a,b) by a carbon-carbon radical coupling of tert-butyl 4-(omega-iodoalkyl)benzoates (7a,b) with 2-substituted-2-cyclopenten-1-ones (5 and 6) utilizing tributyltin hydride, (2) cyclization of either the methyl enol-ethers derived from the 2-cyanocyclopentanones

  在叶酸分子的杂环和桥键区结合修饰的基础上，合成了具有6-5个稠环系统的新型抗叶酸剂6,7-二氢环戊基[d]嘧啶（3a，b和4a，b）。合成方法涉及（1）通过叔碳-碳自由基偶联来合成4- [ω-（2-取代的3-氧代环戊基）烷基]苯甲酸叔丁酯的关键中间体（8a，b和9a，b）利用氢化三丁基锡用2-取代的2-环戊烯-1-酮（5和6）合成4-（ω-碘烷基）苯甲酸丁酯（7a，b），（2）衍生自通过用胍处理2-氰基环戊酮（8a，b）或2-（甲氧基羰基）环戊酮（9a，b）本身可生成带有4-（叔丁氧基羰基）苯基烷基的6,7-二氢环戊基[d]嘧啶（ 11a，b和14a，b），（3）脱保护为相应的羧酸（12a，b和15a，b），和（4）用谷氨酸二乙酯酰胺化和脱酯。用含有三亚甲基（3a）或亚乙基桥（3b）的2,4-二氨基嘧啶稠合的环戊烯化合物发现了有效的二氢叶酸还原酶抑制作用和高度有效的细胞生长抑制作用，但没有
• Synthesis of bicyclic vinyl triazenes by Ficini-type reactions
  作者：Carl Thomas Bormann、Farzaneh Fadaei-Tirani、Rosario Scopelliti、Kay Severin

  DOI：10.1039/d1ob01546j

  日期：——

  Cyclic olefins with triazene functions can display interesting reactivity, but synthetic access to these compounds is limited thus far. Herein, we describe the synthesis of cyclobutenyl triazenes fused to cyclopentanone or cyclohexanone rings. The bicyclic compounds are obtained by Lewis acid-catalyzed [2 + 2] cycloaddition reactions of 1-alkynyl triazenes and enones. In the presence of Me2AlCl, bicyclic

  具有三氮烯官能团的环状烯烃可以表现出有趣的反应性，但到目前为止，合成这些化合物的途径有限。在此，我们描述了与环戊酮或环己酮环稠合的环丁烯基三氮烯的合成。双环化合物是通过路易斯酸催化的 1-炔基三氮烯和烯酮的 [2 + 2] 环加成反应获得的。在 Me 2 AlCl 的存在下，双环 [4.2.0] 三氮烯重排成 [3.2.1] 环系统。后者中的三氮烯官能团可用于进一步的官能化。值得注意的是，我们表明乙烯基三氮烯可以作为 Pd 催化的与芳基硼酸的交叉偶联反应的底物。
• Asymmetric Diels−Alder Reactions of Unsaturated β-Ketoesters Catalyzed by Chiral Ruthenium PNNP Complexes
  作者：Christoph Schotes、Antonio Mezzetti

  DOI：10.1021/ja910039e

  日期：2010.3.24

  Cyclic alpha-unsaturated beta-ketoesters undergo cycloaddition with di- and trisubstituted butadienes to give tetrahydro-1-indanone derivatives with up to 93% ee in the presence of a ruthenium catalyst formed by activation of [RuCl(2)(PNNP)] with (Et(3)P)PF(6) (2 equiv) (PNNP = (1S,2S)-N,N'-bis[o-(diphenylphosphino)benzylidene]cyclohexane-1,2-diamine). The protocol has been used to prepare the estrone derivative (8R, 13S, 14S)-13-tert-butoxycarbonyl-3-methoxy-7,8,1 2,13,15,16-hexahydro-6H-cyclopenta[a]phenanthren-17(14H)-one as a single diastereoisomer with 85% yield and 99% ee after one crystallization step. Its absolute configuration, which has been determined by X-ray diffraction after reduction to the alcohol and esterification with camphanic chloride, is in agreement with the attack of the diene onto the open enantioface of the beta-keto ester (O-O) in the ruthenium complex [Ru(O-O)(PNNP)](2+), whose X-ray structure has been determined.