3-(3'-thienyl)cyclohexanone | 1063681-88-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 杂芳族化合物
• 英文名称: 3-(3'-thienyl)cyclohexanone
• 英文别名: 3-(thiophen-3-yl)cyclohexanone；(3R)-3-thiophen-3-ylcyclohexan-1-one
• CAS: 1063681-88-8
• 化学式: C₁₀H₁₂OS
• 分子量: 180.271
• InChiKey: HXZRGZRUJZSNBX-MRVPVSSYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  12
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  45.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  2-环己烯-1-酮 、 thiophene-3-boronic acid MIDA ester 在 potassium phosphate 、 chlorobis(ethylene)rhodium(I) dimer 、 1,5-anhydro-4-O-diphenylphosphino-2,3,6-trideoxy-L-threo-hex-2-enitol 作用下， 以 1,4-二氧六环 、 水 为溶剂， 反应 16.0h， 以77%的产率得到3-(3'-thienyl)cyclohexanone
  参考文献：
  名称：

  Heteroarylboronates in Rhodium-Catalyzed 1,4-Addition to Enones

  摘要：

  Rhodium(I)-catalyzed 1,4-addition of aryl and alkenylboronic acids to alpha,beta-unsaturated carbonyl compounds is well established, but the transfer of heteroaryl residues in this reaction remains underdeveloped. We have studied heteroaryl MIDA and pinacol boronates as alternatives to the labile boronic acid counterparts. Under racemic conditions, 12 adducts with heteroaryl residues, among them unsubstituted 3- and 4-pyridinyl, 2-furanyl, thienyl, and pyrrolyl groups, were obtained in moderate to excellent yields. The enantioselective version of the reaction proved highly sensitive to the electronic character of the heteroaryl substituents, with boronates carrying electron-rich residues giving modest to high yields but consistently high enantiomeric excesses.

  DOI：

  10.1021/ol502630w

文献信息

• 一种N杂环双膦配体及其合成方法
  申请人：广州大学

  公开号：CN103980312B

  公开（公告）日：2016-09-07

  本发明涉及含氮化合物，具体涉及一种双膦基联喹啉，该其双膦基联喹啉结构为化学式(I)所示，式(I)中R为C1～C5的烷基、C6～C10芳基或者环己基。本发明所述的双膦基联喹啉是以6,6’‑二羟基‑5,5’‑联喹啉与三氟甲磺酸酐合成(R)或(S)‑6,6’‑二(三氟甲磺酰氧基)‑5,5’‑联喹啉，再经由镍催化与二烃基膦烷偶联反应得到。本发明所述的双膦基联喹啉可以作为芳基硼酸对环己烯酮的不对称1,4‑加成反应的催化剂。
• Highly Enantioselective Conjugate Additions of Potassium Organotrifluoroborates to Enones by Use of Monodentate Phosphoramidite Ligands
  作者：Ate Duursma、Jean-Guy Boiteau、Laurent Lefort、Jeroen A. F. Boogers、André H. M. de Vries、Johannes G. de Vries、Adriaan J. Minnaard、Ben L. Feringa

  DOI：10.1021/jo0487810

  日期：2004.11.1

  rhodium-catalyzed asymmetric conjugate addition of potassium organotrifluoroborates to various enones in the absence of water is described. A systematic search for effective catalysts has been performed by use of high-throughput screening methods. Initially, we have screened reaction conditions, catalyst precursors, and focused ligand libraries. In the next stage we have used the monodentate ligand combination

  描述了亚磷酰胺配体在不存在水的情况下在铑催化的有机三氟硼酸钾向各种烯酮的不对称共轭加成中的使用。已经通过使用高通量筛选方法对有效催化剂进行了系统的研究。最初，我们筛选了反应条件，催化剂前体和聚焦的配体库。在下一步中，我们使用了单齿配体组合方法，最后我们通过在机器人中进行并行合成（即时配体库）建立了96种不同的亚磷酰胺的文库，并在环己烯酮的乙烯基化（高达88％对映异构体）中对其进行了测试。过量的ee）和4-苯基-3-丁烯-2-一（最高ee的42％）。通过使用苯基三氟硼酸钾对环己烯酮的丙烯酸化，得到具有99％ee的3-苯基环己酮。
• Rhodium-Catalyzed Asymmetric 1,4-Addition of Heteroaryl Cyclic Triolborate to α,β-Unsaturated Carbonyl Compounds
  作者：Yasunori Yamamoto、Norio Miyaura、Xiao-Qiang Yu

  DOI：10.1055/s-0028-1088198

  日期：2009.4

  Rhodium-catalyzed asymmetric 1,4-additions of electron-deficient heteroaryl groups to α,β-unsaturated carbonyl compounds were established. The reaction resulted in very low yields due to competitive C-B bond cleavage when arylboronic acids, their pinacol esters, or potassium trifluoroborates were used. However, the corresponding lithium heteroaryl(triol)borates afforded 1,4-adducts with high enantioselectivities up to 97% in the presence of a rhodium(I) catalyst chelated with a chiral BINAP or BIPAM ligand.

  铑催化的电子缺乏杂环芳基对α,β-不饱和羰基化合物的非对称1,4-加成反应已被建立。当使用芳基硼酸、其匹那可酯或三氟硼酸钾时，反应的产率非常低，原因是竞争性的C-B键断裂。然而，对应的锂杂环芳基（醇）硼酸盐在铑(I)催化剂与手性BINAP或BIPAM配体形成的配位状态下，能够提供高达97%的优异对映选择性1,4-加成产物。
• Enantioselective rhodium-catalysed 1,4-additions of 2-heteroarylzinc donors using Me-DUPHOS
  作者：Jérôme Le Nôtre、Joseph C. Allen、Christopher G. Frost

  DOI：10.1039/b806098c

  日期：——

  The enantioselective 1,4-addition of 2-(substituted)thienylzinc and 2-furanylzinc reagents has been achieved (up to 99 : 1 er) using a complex derived from [Rh(C2H4)2Cl]2 and Me-DUPHOS.

  利用[Rh(C2H4)2Cl]2 和 Me-DUPHOS 衍生的复合物，实现了 2-（取代的）噻吩基锌和 2-呋喃基锌试剂的对映选择性 1,4-加成（达到 99 : 1 er）。