三丁基(环戊-2-烯-1-基)锡烷 | 58655-77-9

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机过渡后金属化合物
• 中文名称: 三丁基(环戊-2-烯-1-基)锡烷
• 英文名称: Tributyl(cyclopent-2-enyl)stannane
• 英文别名: 3-tributylstannylcyclopentene；(cyclopent-2-enyl)tributyltin；(cyclopent-2-en-1-yl)tributyltin
• CAS: 58655-77-9
• 化学式: C₁₇H₃₄Sn
• 分子量: 357.167
• InChiKey: YNNXRAVLQYPDLR-UHFFFAOYSA-N

物化性质

• 沸点：
  351.2±45.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6.56
• 重原子数：
  18
• 可旋转键数：
  10
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.88
• 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：

  三丁基(环戊-2-烯-1-基)锡烷 、 苯丙酮 在 tin(ll) chloride 作用下， 以 乙腈 为溶剂， 反应 3.0h， 以84%的产率得到(S)-1-((R)-cyclopent-2-enyl)-1-phenylpropan-1-ol
  参考文献：
  名称：

  γ-取代的烯丙基亲核试剂与酮的非对映选择性加成：使用烯丙基三丁基锡烷/氯化亚锡系统高度立体选择性合成叔同烯丙基醇

  摘要：

  γ-取代的烯丙基亲核试剂与酮的非对映选择性加成得到了叔高烯丙基醇。在氯化亚锡 (SnCl(2)) 存在下，三丁基肉桂基锡 1a 与简单酮 2 的反应得到叔高烯丙醇 3，其中包括反形式（基于 Ph 和 OH），具有高非对映选择性。在反应过程中，三丁基肉桂基锡 1a 与 SnCl(2) 进行金属转移，形成活性亲核试剂，暂时认为是肉桂基锡 (II) 物种。环状过渡态 A 是有利的，因为氯化锡 (II) 中心非常能够接受配体。通过使用 BF(3) x OEt(2) 而不是 SnCl(2)，在三丁基肉桂基锡 1a 与酮 2 的反应中获得其他非对映异构体（syn 形式）4。该反应通过无环过渡状态进行，其中 BF(3) 充当路易斯酸以激活酮。当 3-三丁基甲锡烷基环己烯 1b 或 3-三丁基甲锡烷基环戊烯 1c 与 SnCl(2) 一起使用时，观察到具有顺式（基于环链和 OH）的相应高烯丙基醇 6 的高非对映选择性形成。选择性也由环状过渡态

  DOI：

  10.1021/ja0274047
• 作为产物：
  描述：

  环戊烯-1,3-溴-(7CI,9CI) 、 三丁基氯化锡 在 氯化铵 、 锌 作用下， 以 四氢呋喃 、 水 为溶剂， 以40%的产率得到三丁基(环戊-2-烯-1-基)锡烷
  参考文献：
  名称：

  Wurtz-Type Reductive Coupling Reaction of Allyl Bromides and Haloorganotins in Cosolvent/H2O(NH4Cl)/Zn Media as a Route to Allylstannanes and Hexaaryldistannanes

  摘要：

  Twenty-one allylstannanes have been prepared via a simple Wurtz-type coupling reaction of allyl bromides and R3SnX compounds (R = Me, Et, Pr, Bu, Ph; X = Cl, I, OH), Bu2SnCl2, and (BU2SnCl)20 in cosolvent/H2O (NH4Cl saturated) media under the mediation of zinc powder. Also R3SnSnR3 compounds (R = Ph, p- and m-Tol) have been prepared via coupling of triaryltin chlorides. The stereochemical course of the reaction between R3SnCl and (C4H7)Br (C4H7 = alpha-methylallyl, trans- and cis-crotyl) has been extensively studied. Two distinct reactions are involved in the overall process: (i) the coupling reaction, which gives rise stereoselectively to the sole R3SnCH(CH3)CH=CH2 (alpha-isomer), and (ii) the subsequent isomerization of the alpha-isomer furnishing mixtures of (alpha, trans, cis)-isomers. The occurrence of reaction ii depends upon the nature either of the R group or the employed cosolvent. In cyclohexane, the alpha-isomer is exclusively obtained with R = Bu, while with R = Me, Et, and Pr it is found as a major component in the ternary isomeric mixture. In tetrahydrofuran, 2-propanol, acetonitrile, and pyridine, the isomerization occurs to an extent which depends on the polarity and the coordinating ability of the cosolvent itself. The observed stereoselection has been hypothesized to occur through one-electron transfer from the zinc metal to the (C4H7)Br to form stereoselectively an adsorbed CH2=CHCH(CH3)Br.-Zn.+ radical ion which is trapped by the R3SnCl reactant to form the alpha-isomer. Similarly, ditin compounds are thought to be formed by interaction of R3SnCl.-Zn.+ radical ions with R3SnCl molecules.

  DOI：

  10.1021/om00015a025

文献信息

• TRANSFORMATION OF ALLYL STANNANES INTO ALLYL AMINES USING [<i>N</i>-(<i>p</i>-TOLUENESULFONYL)IMINO]-PHENYLIODINANE
  作者：Dae Young Kim、Hee Suk Kim、Young Jae Choi、Joo Yang Mang、Kilsung Lee

  DOI：10.1081/scc-100105125

  日期：2001.1

  Reaction of allyl stannanes with PhI = NTs in the presence of 10mol % of Cu(OTf)2 provides a direct route for the preparation of N-tosylallyl amines in moderate yields.

  烯丙基锡烷与 PhI = NTs 在 10mol% 的 Cu(OTf)2 存在下的反应提供了以中等产率制备 N-甲苯磺酰基烯丙胺的直接途径。
• Isomerization Behavior in the (π-Allyl)palladium(II) Complexes with N²¹,N²²-Bridged Porphyrin Ligands
  作者：Yuko Takao、Tokuji Takeda、Jun-ya Watanabe、Jun-ichiro Setsune

  DOI：10.1021/om0205593

  日期：2003.1.1

  Reactions of (dichloro)palladium(II) complexes of N21,N22-etheno-bridged porphyrins with AgClO4 gave bis(perchlorato)PdII porphyrins. These complexes reacted with allyltributyltins to afford a mixture of cis and trans isomers of (π-allyl)PdII(porphyrin). The trans isomer of (π-C3H5)PdII(porphyrin) preferentially formed by the reaction of (η1-C3H5)SnBu3 gradually isomerized to a cis isomer with exchange

  N 21，N 22-乙撑桥连卟啉的（二氯）钯（II）配合物与AgClO 4的反应得到了双（全氯代）Pd II卟啉。这些络合物与烯丙基三丁基锡反应，得到（π-烯丙基）Pd II（卟啉）的顺式和反式异构体的混合物。的反式异构体（π-C 3 H ^ 5）的Pd II（卟啉）通过反应优先形成（η 1 -C 3 ħ 5）SnBu 3逐渐异构化为顺式异构体，在两个顺位和两个反位之间交换，达到平衡状态，反式/顺式比为3：7。该Δ ģ ⧧ 298值（91.2千焦/摩尔）为这个SYN-SYN-防反交换比所报道的普通氮碱如菲咯啉配体例如大得多。这归因于卟啉配体的空间位阻。通过该顺/反交换（η 1 -烯丙基）钯中间体也以互变观察（η 3 -丁烯基）钯II（卟啉）。室温下在CH中制备的具有反式-2-丁烯基配体和顺式-2-丁烯基配体的异构体之间的比例2氯2为68:32，和η 3 -η 1对在80℃下加温型异构d 6
• Apparent π-Allyl Rotation in the π-(Allyl)palladium(II) Complexes of N²¹,N²²-Bridged Porphyrins
  作者：Yuko Takao、Tokuji Takeda、Jun-ya Watanabe、Jun-ichiro Setsune

  DOI：10.1021/om981000z

  日期：1999.8.1

  of (dichloro)palladium(II) complexes of N21,N22-(etheno) bridged porphyrins with AgClO4 gave bis(perchlorato)Pd(II) porphyrins via (chloro)(perchlorato)Pd(II) porphyrins. While the latter as a dimeric μ-(dichloro)dipalladium(II) form was not reactive, the former reacted with allyltributyltins to afford a mixture of trans and cis isomers of π-(allyl)Pd(II) porphyrins. A trans isomer of π-(C3H5)Pd(II)

  N 21，N 22-（乙基）桥连的卟啉的（二氯）钯（II）配合物与AgClO 4反应，通过（氯）（全氯酮）Pd（II）卟啉反应生成双（高氯酸盐）Pd（II）卟啉。尽管后者为二聚体μ-（二氯）二钯（II）形式不具有反应性，但前者与烯丙基三丁基锡反应生成了π-（烯丙基）Pd（II）卟啉的反式和顺式异构体的混合物。π-（C的反式异构体3 ħ 5）的Pd（II）卟啉通过的反应优先形成（η 1 -C 3 ħ 5）SnBu 3逐渐异构化为顺式异构体，达到反式/顺式比例为3：7的平衡状态。顺式异构体的单晶X射线分析表明，平均Pd-C键距为2.119（3）Å。N3-Pd-N4平面与由四个中碳C5，C10，C15和C20定义的卟啉平面倾斜53.4°。π-（烯丙基）平面相对于N3-Pd-N4平面和卟啉平面分别具有106.8°和53.5°的二面角。
• BuSnCl₃-Mediated Reaction of 3-(Tributylstannyl)cycloalkenes with Aldehydes. Highly<i>erythro</i>-Selective 2-Cyclopentenylation and 2-Cyclohexenylation of Aromatic Aldehydes
  作者：Hideyoshi Miyake、Kimiaki Yamamura

  DOI：10.1246/cl.1992.2221

  日期：1992.11

  3-(Butyldichlorostannyl)cyclopentene and 3-(butyldichlorostannyl)cyclohexene, which are prepared by the transmetalation of corresponding 3-(tributylstannyl)cycloalkene with BuSnCl3, react with aromatic aldehydes to give 2-cycloalkenylated products with excellent erythro-selectivity. However, the corresponding reaction with aliphatic aldehydes proceeded in only moderate erythro-selectivity.

  3-(丁基二氯锡)环戊烯和 3-(丁基二氯锡)环己烯是通过相应的 3-(三丁基锡)环烯烃与 BuSnCl3 发生反金属反应制备的，它们与芳香醛反应生成 2-环烯化产物，具有极佳的赤选择性。然而，与脂肪醛的相应反应仅具有中等的赤式选择性。
• Reaction of allylstannanes with .alpha.,.beta.-unsaturated acyliron complexes: a novel [3 + 2] cycloaddition reaction
  作者：James W. Herndon

  DOI：10.1021/ja00244a061

  日期：1987.5