6-(phenylselanyl)cyclohex-2-en-1-one | 127489-35-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 6-(phenylselanyl)cyclohex-2-en-1-one
• 英文别名: 6-phenylseleno-2-cyclohexen-1-one；6-(phenylseleno)cyclohex-2-enone；6-(phenylselanyl)cyclohex-2-enone；6-phenylselanylcyclohex-2-en-1-one
• CAS: 127489-35-4
• 化学式: C₁₂H₁₂OSe
• 分子量: 251.187
• InChiKey: NKLPSEHZAHVSLY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.72
• 重原子数：
  14
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.25
• 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：

  6-(phenylselanyl)cyclohex-2-en-1-one 在 4-二甲氨基吡啶 、 sodium tetrahydroborate 、 cerium(III) chloride 、 偶氮二异丁腈 、 三正丁基氢锡 作用下， 以 甲醇 、 二氯甲烷 、 苯 为溶剂， 反应 32.17h， 生成 2-环己烯-1-基苯甲酸酯
  参考文献：
  名称：

  Crich, David; Yao, Qingwei; Filzen, G. Fredrick, Journal of the American Chemical Society, 1995, vol. 117, # 46, p. 11455 - 11470

  摘要：

  DOI：
• 作为产物：
  描述：

  2-环己烯-1-酮 、 N,N,N-triphenylselenylisocyanuric acid 在 L-脯氨酰胺 作用下， 以 二氯甲烷 为溶剂， 反应 24.0h， 以76%的产率得到6-(phenylselanyl)cyclohex-2-en-1-one
  参考文献：
  名称：

  N,N,N-三苯基硒基异氰尿酸 (TPSCA)：一种用于醛和酮的 α-苯基硒基化的新型多功能试剂

  摘要：

  已制备、表征并用作亲电子苯基硒基的来源，新的、多功能的试剂 N , N , N - 三苯基硒基异氰脲酸 (TPSCA)。这种相对稳定的化合物用于在温和的反应条件下由 l-脯氨酰胺催化的醛和酮的有效 α-硒基化反应。还研究了醛的有机催化不对称 α-硒基化反应，发现该反应以高对映选择性（96% ee）进行。

  DOI：

  10.1055/s-0035-1560051

文献信息

• [EN] ORGANOCATALYSTS AND METHODS OF USE IN CHEMICAL SYNTHESIS<br/>[FR] ORGANOCATALYSEURS ET PROCEDES D'UTILISATION DE CES DERNIERS DANS LA SYNTHESE CHIMIQUE
  申请人：STC UNM

  公开号：WO2006007586A1

  公开（公告）日：2006-01-19

  The present invention pertains generally to compositions comprising organocatalysts that facilitate stereo-selective reactions and the method of their synthesis and use. Particularly, the invention relates to metal-free organocatalysts for facilitation of stereo-­selective reactions, and the method of their synthesis and use. These compounds have the structure of the Formulas (I) and (II). Where X is independently selected from CH2, N-Ra, O, S or C=O; Y is CH2, N-Ra, O, S or C=O, with the proviso that at least one of X or Y is CH2, and preferably both of X and Y are CH2; Ra is H, an optionally substituted C1-C12 alkyl, preferably an optionally substituted C1-C6 alkyl including a C3-C6 cyclic alkyl group, or an optionally substituted aryl group, preferably an optionally substituted phenyl group; Rb is H, an optionally substituted C1-C12 alkyl, preferably an optionally substituted C1-C6 acyclic or a a C3-C6 cyclic alkyl group, CHO, N(Me)O, CO(S)Ra or the group of Formula (III). Where Rc and Rd are each independently H, F, C1, an optionally substituted C1-C20 alkyl, preferably an optionally substituted C1-C12 alkyl, more preferably a C1-C6 alkyl, and an optionally substituted aryl group, or together Rc and Rd form an optionally substituted carbocyclic or optionally substituted heterocyclic ring; R1 is OH, OR, NR'R', NHC(=O)R, NHSO2R; R2 is H, F, C1, an optionally substituted C1-C20 alkyl, preferably an optionally substituted C1­C6 alkyl, an optionally substituted aryl group or a =O group (which establishes a carbonyl group with the carbon to which =O is attached; R3 is H, OH, F, C1, Br, I, Cl, an optionally substituted C1-C20 alkyl, alkenyl or alkynyl ('hydrocarbyl') group, preferably an optionally substituted C1-C6 alkyl, or an optionally substituted aryl, such that the carbon to which R3 is attached has an R or S configuration; R is H, an optionally substituted C1-C20 alkyl, preferably an optionally substituted C1-C6 alkyl, or an optionally substituted aryl group, R' and R' are each independently H, an optionally substituted C1-C20 alkyl group, preferably an optionally substituted C1-C6 alkyl, or an optionally substituted aryl group; or together R' and R' form an optionally substituted heterocyclic, preferably a 4 to 7 membered optionally substituted heterocyclic group or an optionally substituted heteroaryl ring with the nitrogen to which R' and R' are attached; and wherein said compound is free from a metal catalyst.

  本发明涉及一般包括有机催化剂的组合物，该催化剂促进立体选择性反应以及其合成和使用方法。特别地，本发明涉及无金属有机催化剂以促进立体选择性反应，以及其合成和使用方法。这些化合物具有以下结构的式（I）和（II）。其中X独立地选择自CH2、N-Ra、O、S或C=O；Y为CH2、N-Ra、O、S或C=O，但至少X或Y中的一个为CH2，最好是X和Y都为CH2；Ra为H、可选择地取代的C1-C12烷基，最好是可选择地取代的C1-C6烷基，包括C3-C6环烷基，或可选择地取代的芳基，最好是可选择地取代的苯基；Rb为H、可选择地取代的C1-C12烷基，最好是可选择地取代的C1-C6无环或C3-C6环烷基，CHO、N(Me)O、CO(S)Ra或式（III）的基团。其中Rc和Rd各自独立地为H、F、C1、可选择地取代的C1-C20烷基，最好是可选择地取代的C1-C12烷基，更好地是C1-C6烷基，以及可选择地取代的芳基，或者Rc和Rd一起形成可选择地取代的碳环或可选择地取代的杂环；R1为OH、OR、NR'R'、NHC(=O)R、NHSO2R；R2为H、F、C1、可选择地取代的C1-C20烷基，最好是可选择地取代的C1-C6烷基，可选择地取代的芳基或=O基团（与=O连接的碳形成羰基基团）；R3为H、OH、F、C1、Br、I、Cl、可选择地取代的C1-C20烷基、烯基或炔基（'烃基'），最好是可选择地取代的C1-C6烷基，或可选择地取代的芳基，使得R3连接的碳具有R或S构型；R为H、可选择地取代的C1-C20烷基，最好是可选择地取代的C1-C6烷基，或可选择地取代的芳基，R'和R'各自独立地为H、可选择地取代的C1-C20烷基，最好是可选择地取代的C1-C6烷基，或可选择地取代的芳基；或者R'和R'一起形成可选择地取代的杂环，最好是4到7成员的可选择地取代的杂环基团或与R'和R'连接的氮原子形成可选择地取代的杂芳基环；其中所述化合物不含金属催化剂。
• N-(Phenylseleno)phthalimide: A useful reagent for the α-selenylation of ketones and aldehydes.
  作者：Janine Cossy、Nathalie Furet

  DOI：10.1016/s0040-4039(00)61557-5

  日期：1993.11

  α-phenylselenoketones and α-phenylselenoaldehydes are obtained with a good regioselectivity by treatment of the corresponding ketones or aldehydes with N-(phenylseleno)phthalimide and p-toluenesulfonic acid.

  通过用N-（苯基硒代）邻苯二甲酰亚胺和对甲苯磺酸处理相应的酮或醛，可以获得具有良好区域选择性的α-苯基硒酮和α-苯基硒醛。
• KF/Al2O3 and PEG-400 as a recyclable medium for the selective α-selenation of aldehydes and ketones. Preparation of potential antimicrobial agents
  作者：Francine Novack Victoria、Cátia S. Radatz、Maraisa Sachini、Raquel G. Jacob、Gelson Perin、Wladimir P. da Silva、Eder J. Lenardão

  DOI：10.1016/j.tetlet.2009.09.093

  日期：2009.12

  2-Phenylseleno aldehydes and ketones were selectively obtained using solid-supported catalyst (KF/Al2O3) and PEG-400 as clean, recyclable medium in good to excellent yields. The method was applied in the preparation of highly functionalized 2-phenylseleno citronellal and citronellol, potential bactericide agents. The catalytic system KF/Al2O3 and PEG-400 can be re-used for four times without previous

  使用固体负载的催化剂（KF / Al 2 O 3）和PEG-400作为清洁的可回收介质，以良好或优异的收率选择性地获得了2-苯基硒醛醛和酮。该方法用于制备高度功能化的2-苯基硒代香茅醛和香茅醇（潜在的杀菌剂）。催化系统KF / Al 2 O 3和PEG-400可以重复使用四次，而无需事先处理。
• Direct, Facile Aldehyde and Ketone α-Selenenylation Reactions Promoted by <scp>l</scp>-Prolinamide and Pyrrolidine Sulfonamide Organocatalysts
  作者：Jian Wang、Hao Li、Yujiang Mei、Bihshow Lou、Dingguo Xu、Daiqian Xie、Hua Guo、Wei Wang

  DOI：10.1021/jo0506940

  日期：2005.7.1

  A new catalytic method for direct alpha-selenenylation reactions of aldehydes and ketones has been developed. The results of exploratory studies have demonstrated that L-prolinamide is an effective catalyst for a-selenenylation reactions of aldehydes, whereas pyrrolidine trifluoromethanesulfonamide efficiently promotes reactions of ketones. Under optimized reaction conditions, using N-(phenylseleno)phthalimide as the selenenylation reagent in CH2Cl2 in the presence of L-prolinamide (2 mol %) or pyrrolidine trifluoromethanesulfonamide (10 mol %), a variety of aldehydes and ketones undergo this process to generate a-selenenylation products in high yields. Mechanistic insight into the L-proline and L-prolinamide catalyzed alpha-selenenylation reactions of aldehydes with N-(phenylseleno)phthalimide has come from theoretical studies employing ab initio methods and density functional theory. The results reveal that (1) the rate-limiting step of the process involves attack of the enamine intermediate at selenium in N-(phenylseleno)phthalimide and (2) the energy of the transition state for the reaction catalyzed by prolinamide is lower than that promoted by proline. This result is consistent with experimental observations. The role of hydrogen bond interactions in stabilizing the transition states for this process is also discussed.
• Crich, David; Yao, Qingwei, Journal of the American Chemical Society, 1994, vol. 116, # 6, p. 2631 - 2632
  作者：Crich, David、Yao, Qingwei

  DOI：——

  日期：——