diphenyl(phenylethynyl)stibine | 32584-71-7

• 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: diphenyl(phenylethynyl)stibine
• CAS: 32584-71-7
• 化学式: C₂₀H₁₅Sb
• 分子量: 377.089
• InChiKey: BKHCDWHYZBVJDL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.89
• 重原子数：
  21
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  diphenyl(phenylethynyl)stibine 在 苯基锂 、 copper(I) bromide 作用下， 以 四氢呋喃 为溶剂， 反应 6.25h， 生成 (1-benzyl-4-phenyl-1H-1,2,3-triazol-5-yl)(p-tolyl)methanol
  参考文献：
  名称：

  锑-锂交换反应：三唑基锂与亲电试剂合成1,4,5-三取代-1,2,3-三唑

  摘要：

  在有氧条件下，在CuBr（5 mol％）的存在下，通过乙炔基乙Cu 1与苄基叠氮化物2的Cu催化[3 + 2]环加成反应，合成了三取代5-stibano-1 H -1,2,3-三唑3。在-78°C的氩气气氛下，在无水THF中用等摩尔量的苯基锂（PhLi）处理5-Stibanotriazole 3。随后用各种亲电试剂处理形成含有苄基部分的1,4,5-三取代-1,2,3-三唑5。该反应是用于杂环官能化的锑（Sb）-锂（Li）交换反应的一个新实例。

  DOI：

  10.1016/j.jorganchem.2017.02.019
• 作为产物：
  描述：

  diphenylantimony chloride 在 叔丁基亚氨基-三(二甲氨基)正膦 、 magnesium 作用下， 以 乙醚 、 甲苯 为溶剂， 反应 3.0h， 生成 diphenyl(phenylethynyl)stibine
  参考文献：
  名称：

  Facile Access to Organostibines via Selective Organic Superbase Catalyzed Antimony‐Carbon Protonolysis

  摘要：

  The selective formation of antimony‐carbon bonds via organic superbase catalysis under metal‐ and salt‐free conditions is reported. This novel approach utilizes electron‐deficient stibine, Sb(C6F5)3, to give upon base‐catalyzed reactions with weakly acidic aromatic and heteroaromatic hydrocarbons access to a range of new aromatic and heteroaromatic stibines, respectively, with loss of C6HF5. Also, the significantly less electron‐deficient stibines, Ph2SbC6F5 and PhSb(C6F5)2 smoothly underwent base‐catalyzed exchange reactions with a range of terminal alkynes to generate the stibines of formulae PhSb(C≡CPh)2, and Ph2SbC≡CR [R = C6H5, C6H4‐NO2, COOEt, CH2Cl, CH2NEt2, CH2OSiMe3, Sb(C6H5)2], respectively. These formal substitution reactions proceed with high selectivity as only the C6F5 groups serve as a leaving group to be liberated as C6HF5 upon formal proton transfer from the alkyne. Kinetic studies of the base‐catalyzed reaction of Ph2SbC6F5 with phenyl acetylene to form Ph2SbC≡CPh and C6HF5 suggested the empirical rate law to exhibit a first‐order dependence with respect to the base catalyst, alkyne and stibine. DFT calculations support a pathway proceeding via a concerted σ‐bond metathesis transition state, where the base catalyst activates the Sb‐C6F5 bond sequence through secondary bond interactions.

  DOI：

  10.1002/anie.202407822

文献信息

• Palladium-catalyzed cross-coupling reaction of ethynylstibanes with organic halides
  作者：Naoki Kakusawa、Kouichiro Yamaguchi、Jyoji Kurita

  DOI：10.1016/j.jorganchem.2005.03.021

  日期：2005.6

  The reaction of ethynylstibanes (1a–g) with vinyl halides or triflate in the presence of a palladium catalyst led to the formation of cross-coupling products (5a–g, 10–12) in good to moderate yield, along with homo-coupling products (6a–g). A similar reaction of ethynyldiphenylstibane (1a) with aryl iodides (13a–i) also gave cross-coupling products (14a–i), although the yields were relatively low.

  在钯催化剂的存在下，乙炔基苯乙烯（1a – g）与卤化乙烯或三氟甲磺酸酯的反应导致形成交联产物（5a – g，10 – 12），具有良好至中等的收率以及均相偶联产品（6a–g）。乙炔基二苯基乙b （1a）与芳基碘化物（13a – i）的类似反应也产生交叉偶联产物（14a – i），尽管产量相对较低。交叉偶联产物的产率高度依赖于所用溶剂的性质，当反应在HMPA或胺（如二乙胺和吗啉）中进行时，可获得良好的结果。结果表明，HMPA和用作溶剂的胺可通过锑和氧（对于HMPA）或氮（对于胺）之间的分子间配位作用，促进1上的乙炔基向钯的金属转移。
• Synthesis, antitumor activity, and cytotoxicity of 4-substituted 1-benzyl-5-diphenylstibano-1H-1,2,3-triazoles
  作者：Mizuki Yamada、Tsutomu Takahashi、Mai Hasegawa、Mio Matsumura、Kanna Ono、Ryota Fujimoto、Yuki Kitamura、Yuki Murata、Naoki Kakusawa、Motohiro Tanaka、Tohru Obata、Yasuyuki Fujiwara、Shuji Yasuike

  DOI：10.1016/j.bmcl.2017.11.038

  日期：2018.1

  Trisubstituted 5-organostibano-1H-1,2,3-triazoles (3a–f) were synthesized by the Cu-catalyzed azide-alkyne cycloaddition of various ethynylstibanes (1) with benzylazide (2) in the presence of CuBr (5 mol%) under aerobic conditions. The reaction of 5-stibanotriazoles with HCl afforded C5-unsubstituted 1,2,3-triazoles (4a–f). The antitumor activity of trisubstituted 5-organostibano-1H-1,2,3-triazoles

  在CuBr（5 mol）存在下，通过铜催化的各种乙炔基苯乙烯（1）与苄基叠氮化物（2）的叠氮化物-炔烃环加成反应，合成了三取代的5-organostibano-1 H -1,2,3-三唑（3a–f）。％）在有氧条件下。5-stibanotriazoles与HCl的反应得到C5未取代的1,2,3-三唑（4a–f）。在几种肿瘤细胞系中评估了三取代的5-有机ostibano-1 H -1,2,3-三唑（3a–f）及其5-未取代的1,2,3-三唑（4a–f）的抗肿瘤活性。所有5-stibanotriazoles（3a–f）发挥了出色的抗肿瘤活性。相反，与5-stibanotriazoles（3a-f）相比，分子中不具有二苯基锑基团的5-un取代的1,2,3-三唑（4a-f）表现出非常低的抗肿瘤活性。在这两个系列的化合物中，取代的4-丁基似乎降低了抗肿瘤活性。但是，结果表明，分子中的有机金属（锑）需
• Synthesis of Fully Functionalized 5-Selanyl-1,2,3-triazoles: Copper-Catalysed Three-Component Reaction of Ethynylstibanes, Organic Azides, and Diaryl Diselenides
  作者：Mizuki Yamada、Mio Matsumura、Fumina Takino、Yuki Murata、Yuka Kurata、Masatoshi Kawahata、Kentaro Yamaguchi、Naoki Kakusawa、Shuji Yasuike

  DOI：10.1002/ejoc.201701389

  日期：2018.1.17

  A Cu‐catalysed three‐component reaction of ethynylstibanes, organic azides, and diaryl diselenides under aerobic conditions leads to the formation of fully substituted 5‐selanyl‐1,2,3‐triazoles in moderate to excellent yields. Ethynylstibanes, containing an antimony atom, gave better results than various alkynes containing other typical elements, such as silicon, tin, and tellurium.

  在有氧条件下，铜催化的乙炔基乙炔类，有机叠氮化物和二芳基二硒化物的三组分反应导致完全取代的5-癸二烯丙基1,2,3-三唑的形成，产率中等至优异。与含有其他典型元素（例如硅，锡和碲）的各种炔烃相比，含有锑原子的乙炔基斯蒂班尼类化合物的结果更好。
• Microwave-Assisted Cross-Coupling Reaction of Alkynylstibanes with Aryl Iodides in the Presence of Ammonium Salt
  作者：Naoki Kakusawa、Jyoji Kurita

  DOI：10.1248/cpb.53.1369

  日期：——

  The scope of microwave-assisted coupling reaction of alkynylstibane and aryl iodides to form diarylalkynes is presented. Highly efficient reaction took place smoothly in dimethyl sulfoxide in the presence of cetyltrimethylammonium bromide with much shorter time (1 min) and lower catalyst loading (0.5 mol%) than the conventional method (heating for 24 h with 10 mol% catalyst).

  提出了炔基锡烷与芳基碘化物进行微波辅助偶联反应生成二芳基炔烃的范围。在十六烷基三甲基溴化铵存在下，在二甲基亚砜中平稳高效地进行了反应，比传统方法（用10摩尔％的催化剂加热24小时）的时间短得多（1分钟），催化剂负载量低（0.5摩尔％）。
• Palladium-catalyzed cross-coupling reactions between 1-alkynylstibines and acyl chlorides
  作者：Naoki Kakusawa、Kouichiro Yamaguchi、Jyoji Kurita、Takashi Tsuchiya

  DOI：10.1016/s0040-4039(00)00554-2

  日期：2000.5

  1-Alkynyldiphenylstibines react with acyl chlorides in dichloroethane in the presence of a palladium(0) or (II) catalyst to afford alkynyl ketones by cross-coupling reaction in good to moderate yields. These reactions are highly substituent-selective in that only the alkynyl group could be transferred from the antimony compounds, even in the presence of a large excess of acyl chlorides.

  1-炔基二苯基stibines在钯（0）或（II）催化剂存在下，在二氯乙烷中与酰氯反应，以良好的中度收率通过交叉偶联反应提供炔基酮。这些反应是高度取代基选择性的，因为即使在存在大量过量的酰氯的情况下，也只能从锑化合物中转移出炔基。