2-(phenylseleno)-2-cyclopenten-1-one | 71996-27-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 2-(phenylseleno)-2-cyclopenten-1-one
• 英文别名: 2-(phenylseleno)cyclopent-2-enone；2-(phenylselenenyl)-2-cyclopentenone；2-Cyclopenten-1-one, 2-(phenylseleno)-；2-phenylselanylcyclopent-2-en-1-one
• CAS: 71996-27-5
• 化学式: C₁₁H₁₀OSe
• 分子量: 237.16
• InChiKey: MFEPZVBBBRZLHD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.26
• 重原子数：
  13
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.18
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  2-(phenylseleno)-2-cyclopenten-1-one 在 臭氧 、 二乙胺 作用下， 生成 2,3-二甲基-2-环戊烯酮
  参考文献：
  名称：

  Synthetic applications of 2-phenylselenenyl enones. Selective formation of exocyclic or endocyclic enones from a common intermediate

  摘要：

  DOI：

  10.1021/jo01301a046
• 作为产物：
  描述：

  2-重氮基环戊酮 在 sodium carbonate 作用下， 以 二氯甲烷 、 xylene 为溶剂， 生成 2-(phenylseleno)-2-cyclopenten-1-one
  参考文献：
  名称：

  的反应α -diazoketones用苯硒基氯。α-氯-和α-苯基硒烯基-αβ-不饱和酮的新合成

  摘要：

  在室温下，α-重氮酮与苯基硒烯基氯反应，得到α-氯-α-苯基硒烯基酮；在结构上允许的情况下，这些加合物可以通过消除反应转化为α-氯代或α-苯基硒烯基-α，β-不饱和酮。

  DOI：

  10.1039/c39800000506

文献信息

• Formation of 2-phenylselenenylenones and 2-haloenones from enones. Mechanistic and synthetic aspects, X-ray crystal structures of intermediates
  作者：Lars Engman、Karl Wilhelm Törnroos

  DOI：10.1016/0022-328x(90)80171-u

  日期：1990.7

  by X-ray diffraction. Although this and similar compounds were readily dehydrohalogenated to give vinylic selenides, they were ruled out as intermediates in the synthesis of 2-phenylselenenylenones from enones and the 1:1 complex of PhSeCl and pyridine.

  通过X射线衍射确定反式-3-氯-2-苯基硒烯基环己酮（1）的结构。尽管该化合物和类似化合物很容易脱卤化氢得到乙烯基硒化物，但它们被排除为由烯酮与PhSeCl和吡啶的1：1络合物合成2-苯基硒烯烯烯酮的中间体。
• 1,2- versus 1,4-Addition to α-donor-cyclopenten-1-ones; a comparison of calculated and experimental data †
  作者：Hanna S. H. Gautun、Rolf Carlson、Per N. Skancke

  DOI：10.1039/a905444h

  日期：——

  A series of α-donor-cyclopenten-1-ones, 1 (α-donor; X = H, Cl, Br, OMe, pyrrolidin-1-yl, SPh and SePh) were treated with methyllithium, lithium dimethylcuprate and cyanomethyllithium in tetrahydrofuran at –78 °C. The reactions between 1 and methyllithium gave 1,2-adducts in 28–75% yield. No trace of the corresponding 1,4-adduct was observed. By treatment of 1 with lithium dimethylcuprate only 1,4-addition was obtained in 51–76% yield, except for X = OMe or pyrrolidin-1-yl, which gave no reaction at all. In the reactions between 1 and cyanomethyllithium the 1,2-adducts were the main products (43–60%), but varying amounts of 1,4-adducts (8–30%) were also formed. The products formed have been fully characterized. Net atomic charges obtained by density functional theory (DFT) calculations of the lithiated cations of 1 with X = H, Cl, Br or OMe showed very small differences between the substituted and unsubstituted systems for all X, except for X = OMe. In this case the C2 position was positive rather than negative. The C3 position was found to be significantly more negative. The calculated relative energies of the methylated and cyanomethylated 1,2- and 1,4-adducts with X = H, Cl, Br and OMe indicated that the 1,4-adducts were thermodynamically favoured by 8 to 12 kcal mol–1 for all but one case. In the cyanomethylation of 1 with X = OMe the 1,2-adduct was predicted to be favoured by 12 kcal mol–1. Thus, the predominance of 1,2-attack in the reactions involving methyllithium and cyanomethyllithium cannot be explained by the relative thermodynamic stabilities of the products.

  一系列α-给体-环戊烯-1-酮，1（α-给体；X = H、Cl、Br、OMe、吡咯烷-1-基、SPh和SePh）在-78°C下与甲基锂、二甲基铜锂和氰基甲基锂在四氢呋喃中进行反应。1与甲基锂的反应生成1,2-加合物，产率为28-75%。未观察到相应的1,4-加合物。1与二甲基铜锂的反应仅得到1,4-加成产物，产率为51-76%，除了X = OMe或吡咯烷-1-基，这些情况下根本不发生反应。1与氰基甲基锂的反应中，1,2-加合物是主要产物（43-60%），但也形成了不同数量的1,4-加合物（8-30%）。形成的产物已完全表征。通过密度泛函理论（DFT）计算得到的1的锂化阳离子（X = H、Cl、Br或OMe）的净原子电荷显示，所有X的取代和未取代体系之间的差异非常小，除了X = OMe的情况。在这种情况下，C2位置是正的而不是负的。C3位置显著更加负电。计算得到的甲基化和氰基甲基化的1,2-和1,4-加合物（X = H、Cl、Br和OMe）的相对能量表明，除了一个情况外，1,4-加合物在热力学上更优，优于8到12 kcal/mol。在X = OMe的1的氰基甲基化中，预测1,2-加合物更优，优于12 kcal/mol。因此，涉及甲基锂和氰基甲基锂的反应中1,2-攻击的主导地位不能通过产物的相对热力学稳定性来解释。
• Oxidation of Olefins into α-Phenylseleno Carbonyl Compounds. Highly Regioselective<i>anti</i>-Markownikoff Type Oxidation of Allylic Alcohol Derivatives
  作者：Makoto Shimizu、Ryo Takeda、Isao Kuwajima

  DOI：10.1246/bcsj.54.3510

  日期：1981.11

  (C6H5Se)2–(C6H5SeO)2O system, oxoselenenylation reactions of C=C bonds have been examined with allylic and homoallylic alcohol derivatives, and substituted cyclohexenes, and allyl t-butyldimethylsilyl ethers are found to undergo regioselective conversion into β-siloxy α-phenylseleno carbonyl compounds in high yields.

  通过使用 (C6H5Se)2–t-BuOOH 或 (C6H5Se)2–(C6H5SeO)2O 系统，C=C 键的氧代硒烯基化反应已经用烯丙醇和高烯丙醇衍生物、取代的环己烯和烯丙基叔丁基二甲基甲硅烷基醚进行了研究发现以高产率进行区域选择性转化为 β-甲硅烷氧基 α-苯基硒羰基化合物。
• Synthesis of 2,2-Disubstituted Pentalenes and Indenes by a Useful Modification to Nakamura’s DMCP [3+2]-Cycloaddition Protocol
  作者：Thomas Pettus、Todd Wenderski、Vincent DeNatale

  DOI：10.1055/s-0029-1217755

  日期：2009.10

  A two-pot tactic is presented to reach the oxidized 2,2-dimethyl-substituted pentalene and indene ring systems.

  提出了一种两锅法以得到氧化的 2,2-二甲基取代的五环戊二烯和茚环体系。
• Vinyl Anion Equivalents. Part IV. Efficient Synthesis of 2-(1-Hydroxyalkyl)-2-cyclopenten-1-ones
  作者：Shinya Kusuda、Yoshio Ueno、Takeshi Toru

  DOI：10.1246/bcsj.66.2720

  日期：1993.9

  Aldol reactions of lithium enolates resulted from conjugate additions of tributylstannyllithium to 2-(phenylseleno)-2-cyclopenten-1-one provides 2-(1-hydroxyalkyl)-2-cyclopenten-1-ones in high yields. Significantly good 1,4-asymmetric induction took place in analogous aldol reactions starting with chiral 4-[(t-butyldimethylsilyl)oxy]-2-(phenylseleno)-2-cyclopenten-1-one.

  烯醇锂的羟醛反应由三丁基锡锂与 2-(苯基硒基)-2-环戊烯-1-酮的共轭加成产生，以高产率提供 2-(1-羟基烷基)-2-环戊烯-1-酮。在以手性 4-[(叔丁基二甲基甲硅烷基)氧基]-2-(苯基硒基)-2-环戊烯-1-酮开始的类似醛醇反应中发生了显着良好的1,4-不对称诱导。