三丁基(2-甲基丁-2-烯基)锡烷 | 115991-75-8

• 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(2-甲基丁-2-烯基)锡烷
• 英文名称: 2-methyl-2-butenyltributyltin
• 英文别名: Tributyl(2-methylbut-2-EN-1-YL)stannane；tributyl(2-methylbut-2-enyl)stannane
• CAS: 115991-75-8
• 化学式: C₁₇H₃₆Sn
• 分子量: 359.183
• InChiKey: NGQZOIDPPZMEBA-UHFFFAOYSA-N

物化性质

• 沸点：
  346.3±35.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6.8
• 重原子数：
  18
• 可旋转键数：
  11
• 环数：
  0.0
• 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：

  二苯基溴甲烷 、 三丁基(2-甲基丁-2-烯基)锡烷 在 zinc chloride diethyl ether 作用下， 以 二氯甲烷 为溶剂， 反应 0.17h， 以90%的产率得到2,3-Dimethyl-4,4-diphenyl-1-butene
  参考文献：
  名称：

  Radical Reaction Initiated and Stereocontrolled by Zinc Chloride

  摘要：

  The reaction of allyltributyltin with methyl 2-[N-((4S)-4-(1-methylethyl)-2-oxazolidinone-3-carbamoyl)amino]-2-bromoacetate (5a) was accelerated at -50 degrees C in the presence of AIBN and stopped in the presence of galvinoxyl, indicating that the reaction proceeds through a radical mechanism. The reaction was accelerated dramatically at -78 degrees C in the presence of ZnCl2 . OEt2, and the ZnCl2-mediated reaction was stopped in the presence of galvinoxyl. In the presence of 2 equiv ZnCl2 . OEt2, the reaction afforded methyl (2R)-2-[N-((4S)-4-(1-methylethyl)-2-oxazolidinone-3- carbamoyl)amino]4-pentenoate {6a(R)} with high diastereoselectivity (93:7). Taken together, ZnCl2 . OEt2 works as a radical initiator as well as chelating agent.

  DOI：

  10.3987/com-97-s(n)71
• 作为产物：
  描述：

  三丁基氯化锡 、 1-溴-3-甲基-2-丁烯 在 氯化铵 、 锌 作用下， 以 四氢呋喃 、 水 为溶剂， 生成 三丁基(3-甲基-2-丁烯基)锡 、 三丁基(2-甲基丁-2-烯基)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

• Wurtz-Type Reductive Coupling Reaction of Allyl Bromides and Haloorganotins in Cosolvent/H2O(NH4Cl)/Zn Media as a Route to Allylstannanes and Hexaaryldistannanes
  作者：Friederike von Gyldenfeldt、Daniele Marton、Giuseppe Tagliavini

  DOI：10.1021/om00015a025

  日期：1994.3

  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.
• Radical Reaction Initiated and Stereocontrolled by Zinc Chloride
  作者：Yoshinori Yamamoto、Setsuko Onuki、Masatoshi Yumoto、Naoki Asao

  DOI：10.3987/com-97-s(n)71

  日期：——

  The reaction of allyltributyltin with methyl 2-[N-((4S)-4-(1-methylethyl)-2-oxazolidinone-3-carbamoyl)amino]-2-bromoacetate (5a) was accelerated at -50 degrees C in the presence of AIBN and stopped in the presence of galvinoxyl, indicating that the reaction proceeds through a radical mechanism. The reaction was accelerated dramatically at -78 degrees C in the presence of ZnCl2 . OEt2, and the ZnCl2-mediated reaction was stopped in the presence of galvinoxyl. In the presence of 2 equiv ZnCl2 . OEt2, the reaction afforded methyl (2R)-2-[N-((4S)-4-(1-methylethyl)-2-oxazolidinone-3- carbamoyl)amino]4-pentenoate 6a(R)} with high diastereoselectivity (93:7). Taken together, ZnCl2 . OEt2 works as a radical initiator as well as chelating agent.