benzothiophen-2-yllithium | 50779-55-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并噻吩类
• 英文名称: benzothiophen-2-yllithium
• 英文别名: 2-lithiobenzo[b]thiophene；benzo[b]thiophen-2-yllithium；2-benzo[b]thienyllithium
• CAS: 50779-55-0
• 化学式: C₈H₅LiS
• 分子量: 140.135
• InChiKey: CLXKDEZNTHPJDN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.32
• 重原子数：
  10
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  28.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  benzothiophen-2-yllithium 在 sodium perborate 、 sodium tetrahydroborate 作用下， 以 四氢呋喃 、 二氯甲烷 、 溶剂黄146 为溶剂， 反应 2.17h， 生成 benzothiophenesulfone-2-methyl N-(p-chlorophenyl)carbamate
  参考文献：
  名称：

  The 1,1-Dioxobenzo[b]thiophene-2-ylmethyloxycarbonyl (Bsmoc) Amino-Protecting Group

  摘要：

  Full details are presented for use of the Bsmoc amino-protecting group for both solid phase and rapid continuous solution syntheses. Application to the latter methodology represents a significant improvement over the corresponding Fmoc-based method for rapid solution synthesis due to the opportunity to use water or saturated sodium-chloride solution rather than an acidic phosphate buffer to remove all byproducts, with consequent cleaner phase separation and higher yields of the growing peptide. Comparison of the Bsmoc and Bspoc functions showed that the former, because of steric hindrance, does not suffer from the competitive or premature deblocking observed with the Bspoc system. Because of its incorporation of a styrene chromophore, resin loading of Bsmoc amino acids could be followed as has previously been shown for the Fmoc analogues. Applications of Bsmoc chemistry to peptide sequences incorporating the base sensitive Asp-Gly unit gave less contamination due to aminosuccinimide formation than comparable syntheses involving standard Fmoc chemistry because a weaker or less concentrated base could be used in the deblocking step. Experimental details are presented for building up peptides in solution via the continuous methodology. Deblockings involved the use of insoluble piperazino silica as well as the polyamine TAEA which simplified aqueous separation of the growing, but nonisolated peptide product, from excess acylating agent and other side products formed in the deblocking process. By the appropriate choice of base, one can act selectively at either site of a molecule which incorporates both beta-elimination and Michael acceptor sites as protective units (Bsmoc vs Fm and Fmoc vs Bsm).

  DOI：

  10.1021/jo982140l
• 作为产物：
  描述：

  2-溴苯并噻吩 在 正丁基锂 作用下， 以 正己烷 为溶剂， 生成 benzothiophen-2-yllithium
  参考文献：
  名称：

  Synthesis of Benzosiloles by Intramolecular anti-Hydroarylation via ortho-C–H Activation of Aryloxyethynyl Silanes

  摘要：

  Straightforward synthesis of benzosiloles was achieved by the invention of Pd/acid-catalyzed intramolecular anti-hydroarylation of aryloxyethynyl(aryl)-silanes via ortho-C-H bond activation. The aryloxy group bound to the ethynyl carbon is the key factor for this transformation.

  DOI：

  10.1021/jacs.7b08055

文献信息

• Functional-Group-Tolerant, Nickel-Catalyzed Cross-Coupling Reaction for Enantioselective Construction of Tertiary Methyl-Bearing Stereocenters
  作者：Hanna M. Wisniewska、Elizabeth C. Swift、Elizabeth R. Jarvo

  DOI：10.1021/ja4034999

  日期：2013.6.19

  The first Negishi nickel-catalyzed stereospecific cross-coupling reaction of secondary benzylic esters is reported. A series of traceless directing groups is evaluated for ability to promote cross-coupling with dimethylzinc. Esters with a chelating thioether derived from commercially available 2-(methylthio)acetic acid are most effective. The products are formed in high yield and with excellent stereospecificity

  报道了第一个根岸镍催化仲苄酯的立体定向交叉偶联反应。评估了一系列无痕导向基团促进与二甲基锌交叉偶联的能力。由市售的 2-(甲硫基)乙酸衍生的具有螯合硫醚的酯是最有效的。形成的产品收率高，且具有优异的立体定向性。该反应可耐受多种官能团，包括烯烃、炔烃、酯、胺、酰亚胺以及 O-、S- 和 N- 杂环。这种转化的实用性在视黄酸受体激动剂和脂肪酸酰胺水解酶抑制剂的对映选择性合成中得到强调。
• Ruthenium‐Catalyzed Direct Asymmetric Reductive Amination of Diaryl and Sterically Hindered Ketones with Ammonium Salts and H ₂
  作者：Le' an Hu、Yao Zhang、Qing‐Wen Zhang、Qin Yin、Xumu Zhang

  DOI：10.1002/anie.201915459

  日期：2020.3.23

  A Ru-catalyzed direct asymmetric reductive amination of ortho-OH-substituted diaryl and sterically hindered ketones with ammonium salts is reported. This method represents a straightforward route toward the synthesis of synthetically useful chiral primary diarylmethylamines and sterically hindered benzylamines (up to 97 % yield, 93->99 % ee). Elaborations of the chiral amine products into bioactive

  报道了钌盐对铵基取代的邻羟基取代的二芳基和位阻酮的Ru催化的直接不对称还原胺化反应。该方法代表了合成合成有用的手性伯二芳基甲基胺和位阻苄胺的直接途径（产率高达97％，ee达93-> 99％）。通过操纵可除去和可转化的-OH基团，证明了将手性胺产物精制为生物活性化合物和手性配体。
• Copper-catalysed α-selective allylic alkylation of heteroaryllithium reagents
  作者：Carlos Vila、Valentín Hornillos、Martín Fañanás-Mastral、Ben L. Feringa

  DOI：10.1039/c4ob01896f

  日期：——

  2-Allyl-substituted thiophenes and furans are synthesised efficiently in a direct procedure using 2-heteroaryllithium reagents and allyl bromides and chlorides catalysed by ligand-free copper(i). The reactions take place under mild conditions, with excellent α-selectivity, high functional group tolerance and good yields for the S_N2 products.

  2-烯丙基取代噻吩和呋喃可通过使用2-杂环基锂试剂和烯丙基溴化物和氯化物，在无配体铜(i)催化下，通过直接程序高效合成。这些反应在温和条件下进行，具有优异的α-选择性，高官能团耐受性，并且对S_N2产物有良好的产率。
• METHOD FOR PREPARING BORINIC ACID DERIVATIVES AND NOVEL BORINIC ACID DERIVATIVES
  申请人：MANAC INC.

  公开号：US20150105562A1

  公开（公告）日：2015-04-16

  The present invention relates to a method for preparing borinic acid derivatives and novel borinic acid derivatives. The preparing method of the present invention provides borinic acid derivatives of general formula (2): (Ar 2 B(OH)   (2) wherein Ar is the same as defined in the description and claims, selectively and in a high yield by reacting a compound of general formula (1): Ar-M,   (1) wherein Ar and M are the same as defined in the description and claims, with tri-t-butyl borate and then hydrolyzing the reaction product.

  这项发明涉及一种制备硼酸衍生物和新型硼酸衍生物的方法。本发明的制备方法提供了一般式（2）的硼酸衍生物： （Ar）2B(OH)   （2） 其中 Ar与描述和权利要求中定义的相同，通过将一般式（1）的化合物： Ar-M，  （1） 其中 Ar和M与描述和权利要求中定义的相同，与三叔丁基硼酸酯反应，然后水解反应产物，以高产率选择性地制备硼酸衍生物。
• Diphenylparabanic Acid as a Synthon for the Synthesis of α-Diketones and α-Ketocarboxylic Acids
  作者：Nobuko Watanabe、Mitsutaka Hamano、Shota Todaka、Takahiro Asaeda、Hisako K. Ijuin、Masakatsu Matsumoto

  DOI：10.1021/jo202304x

  日期：2012.1.6

  Diphenylparabanic acid was found to react with >2 equiv of organolithiums at −78 °C to effectively give the corresponding symmetrical α-diketones. However, upon treatment with 1 equiv of organolithium, the parabanic acid gave mainly 5-substituted 5-hydroxyimidazolidine-2,4-diones. On the other hand, Grignard reagents were less reactive toward the parabanic acid at low temperature, and selectively gave

  发现二苯基对羟基苯甲酸在-78°C下与> 2当量的有机锂反应，可以有效地产生相应的对称α-二酮。然而，用1当量的有机锂处理后，对羟基苯甲酸主要产生5-取代的5-羟基咪唑烷-2，4-二酮。另一方面，即使使用多于1当量的试剂，格氏试剂在低温下对对羟基苯甲酸的反应性较小，并选择性地得到相应的5-羟基咪唑烷-2，4-二酮。串联过程中，首先将对羟基苯甲酸与格氏试剂反应，然后与有机锂一锅反应，有效地得到了不对称的α-二酮。5-取代的5-羟基咪唑烷-2,4-二酮可用作制备α-酮羧酸以及不对称α-二酮的通用前体。