(Z)-1,4-diphenyl-1-(tributylstannyl)but-1-en-3-yne | 926317-97-7

• 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: (Z)-1,4-diphenyl-1-(tributylstannyl)but-1-en-3-yne
• CAS: 926317-97-7；204651-35-4
• 化学式: C₂₈H₃₈Sn
• 分子量: 493.32
• InChiKey: UGBPNPZEBZOABC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.93
• 重原子数：
  29
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.32
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为产物：
  描述：

  苯基乙炔三丁基锡 、 苯乙炔 在 catalyst: Pd-complex of Ph₂PC₆H₄-2-CH=NCH₂CH₂Ph 作用下， 以 四氢呋喃 为溶剂， 生成 (Z)-1,4-diphenyl-1-(tributylstannyl)but-1-en-3-yne 、 tributyl[(1Z)-2,4-diphenyl-1-buten-3-ynyl]stannane
  参考文献：
  名称：

  钯-亚氨基膦催化剂用于有机锡的反应

  摘要：

  发现由亚氨基膦配体配位的钯配合物是有机锡与芳基卤化物偶联的显着活性催化剂。机理研究表明，炔基锡烷的反应是通过前所未有的催化循环进行的，该循环涉及将有机锡烷氧化加成到Pd（0）-亚氨基膦配合物中。已证明该催化剂也可用于炔烃的羰基合成和有机锡的均偶联反应。

  DOI：

  10.1016/s0022-328x(98)01056-0

文献信息

• A Drastic Effect of TEMPO in Zinc‐Catalyzed Stannylation of Terminal Alkynes with Hydrostannanes via Dehydrogenation and Oxidative Dehydrogenation
  作者：Yuichi Kai、Shinya Oku、Tomohiro Tani、Kyoko Sakurai、Teruhisa Tsuchimoto

  DOI：10.1002/adsc.201900540

  日期：2019.9.17

  With a system consisting of a catalytic zinc Lewis acid, pyridine, and TEMPO in a nitrile medium, terminal alkynes coupled with HSnBu3, providing alkynylstannanes with structural diversity. The resulting alkynylstannane, without being isolated, could be directly used for Pd‐ and Cu‐catalyzed transformations to deliver internal alkynes and more intricate tin‐atom‐containing molecules. Mechanistic studies

  通过在腈介质中由催化锌路易斯酸，吡啶和TEMPO组成的系统，末端炔烃与HSnBu 3偶联，可提供具有结构多样性的炔基锡烷。生成的炔基锡烷无需分离即可直接用于Pd和Cu催化的转化，以传递内部炔烃和更复杂的含锡原子的分子。机制研究表明TEMPOSnBu 3原位形成从TEMPO和HSnBu 3作品stannylate末端炔与锌催化剂的协作，并且这两个脱氢和氧化脱氢工艺的被唯一地涉及在一个单一的反应。
• Ruthenium-Catalyzed Addition of Terminal Alkynes to Alkynylstannanes with Migration of the Stannyl Group
  作者：Eiji Shirakawa、Kouji Nakayama、Ryotaro Morita、Teruhisa Tsuchimoto、Yusuke Kawakami、Toshiaki Matsubara

  DOI：10.1246/bcsj.79.1963

  日期：2006.12

  In the presence of a catalytic amount of a ruthenium complex coordinated with PBu3, alkynylstannanes (R1C≡CSnBu3) were found to accept the addition of terminal alkynes (R2C≡CH) with a 1,2-shift of the stannyl group to give (E)- and (Z)-1-tributylstannylbut-1-en-3-ynes (Bu3SnC(R1)=CHC≡CR2). Various combinations of substrates having an aromatic and/or aliphatic substituent can be used, and the stereochemical outcome depends largely on the character of these substituents. The reaction of aliphatic terminal alkynes proceeds stereoselectively, and substituent R1 on the alkynylstannanes determines the configuration: E for R1 = alkyl and Z for R1 = aryl. In contrast, the reaction of arylacetylenes gave a mixture of stereoisomers irrespective of the character of substituent R1 on the alkynylstannane. Ruthenium–β-stannylvinylidene complexes generated from a ruthenium complex and an alkynylstannane with migration of the stannyl group are likely to be key intermediates, which accept addition of the C–H bond of terminal alkynes to give the corresponding stannylenynes. DFT calculation clearly shows that the 1,2-shift of the stannyl group on formation of ruthenium–β-stannylvinylidene complexes is more facile than the corresponding 1,2-hydrogen shift of the coordinating terminal alkynes. The effect of the substituents on the stereoselectivity also is discussed based on the calculation.

  在以PBu3配位的钌络合物的催化作用下，炔基锡烷（R1C≡CSnBu3）可以接受端炔（R2C≡CH）的加成，伴随锡基团的1,2-迁移，生成(E)-和(Z)-1-三丁基锡基丁-1-烯-3-炔（Bu3SnC(R1)=CHC≡CR2）。可以使用具有芳香和/或脂肪族取代基的各种底物组合，立体化学结果主要取决于这些取代基的性质。脂肪族端炔的反应具有立体选择性，且炔基锡烷上的取代基R1决定构型：R1为烷基时得到E构型，R1为芳基时得到Z构型。相比之下，芳基乙炔的反应产生立体异构体的混合物，与炔基锡烷上取代基R1的性质无关。由钌络合物和炔基锡烷经锡基团迁移生成的钌-β-锡基亚甲基络合物可能是关键中间体，它们接受端炔的C-H键加成生成相应的锡基烯炔。DFT计算清楚地表明，在形成钌-β-锡基亚甲基络合物时，锡基团的1,2-迁移比配位端炔的相应1,2-氢迁移更容易进行。文中还基于计算讨论了取代基对立体选择性的影响。
• Palladium−Iminophosphine-Catalyzed Alkynylstannylation of Alkynes
  作者：Hiroto Yoshida、Eiji Shirakawa、Takuya Kurahashi、Yoshiaki Nakao、Tamejiro Hiyama

  DOI：10.1021/om000828u

  日期：2000.12.1

  A palladium complex coordinated by an iminophosphine ligand was found to catalyze the addition of alkynylstannanes to a carbon-carbon triple bond of various alkynes in moderate to good yields with exclusive syn selectivity. The alkynyl group in the stannanes was attached: mainly to the internal carbon of terminal alkynes, except for 1-alkyn-3-ones and alkynoates, where the alkynyl group was connected to the terminal carbon. Steric bulk of the ligand markedly influenced on the regioselectivity and reaction rate: an iminophosphine with a bulkier imino moiety accelerated the alkynylstannylation with higher regioselectivity. On the basis of these observations, the. mechanism of the present reaction is discussed.
• Carbostannylation of Alkynes Catalyzed by an Iminophosphine−Palladium Complex
  作者：Eiji Shirakawa、Hiroto Yoshida、Takuya Kurahashi、Yoshiaki Nakao、Tamejiro Hiyama

  DOI：10.1021/ja974206k

  日期：1998.4.1