4,4-dimethyl-1-(tributylstannyl)-2-pentyne | 144241-73-6

• 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
• 英文名称: 4,4-dimethyl-1-(tributylstannyl)-2-pentyne
• CAS: 144241-73-6
• 化学式: C₁₉H₃₈Sn
• 分子量: 385.221
• InChiKey: MLSFXFFUTJKKKU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.66
• 重原子数：
  20
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.68
• 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：

  4,4-dimethyl-1-(tributylstannyl)-2-pentyne 、 [(4-Deuteriophenyl)-[(4-deuteriophenyl)-(trifluoromethylsulfonyloxy)-lambda3-iodanyl]oxy-lambda3-iodanyl] trifluoromethanesulfonate 以 氯仿 为溶剂， 生成 4-Deuterio-2-(4,4-dimethylpent-2-ynyl)-1-iodobenzene
  参考文献：
  名称：

  Reaction of .mu.-oxobis[(trifluoromethanesulfonato)(phenyl)iodine(III)] with group 14 propargyl derivatives and a propargyl ether

  摘要：

  The treatment of 4,4-dimethyl-l-(trimethylsilyl)-2-pentyne (4a) or 4,4-dimethyl-l-(tributylstannyl)-2-pentyne (4b) with mu-oxobis[(trifluoromethanesulfonato)(phenyl)iodine(III)] (2) gives 4,4-dimethyl-l-(2-iodophenyl)-2-pentyne (9). Deuterium labeling has confirmed that propargylation of 2 occurs ortho to the position originally occupied by the I(III). The addition of 2 equiv of 4a to 2 at -80-degrees-C results in 2 equiv each of 9, trimethylsilyl triflate (10), and tert-butyballene (11) and 1 equiv of hexamethyldisiloxane (12); in contrast, the addition of 2 equiv of 4b to 2 at -30-degrees-C results in 2 equiv each of 9 and tributylstannyl triflate (16). A mechanism that explains these product ratios is proposed. The reaction of 2-o,o'-d2 and 4b shows the negligible intramolecular kinetic isotope effect (0.99 +/- 0.01) expected for what is in effect a Claisen rearrangement. The addition of 2 to 2-butynyl (trimethylsilyl)methyl ether (20) affords the single product 21 resulting from anti addition and control of regiochemistry by the ether oxygen. Attempts to desilylate 21 to an allenyl triflate result in the regeneration of the propargyl ether 20.

  DOI：

  10.1021/jo00050a024

文献信息

• Reaction of .mu.-oxobis[(trifluoromethanesulfonato)(phenyl)iodine(III)] with group 14 propargyl derivatives and a propargyl ether
  作者：Daniel A. Gately、Thomas A. Luther、Jack R. Norton、Mary M. Miller、Oren P. Anderson

  DOI：10.1021/jo00050a024

  日期：1992.11

  The treatment of 4,4-dimethyl-l-(trimethylsilyl)-2-pentyne (4a) or 4,4-dimethyl-l-(tributylstannyl)-2-pentyne (4b) with mu-oxobis[(trifluoromethanesulfonato)(phenyl)iodine(III)] (2) gives 4,4-dimethyl-l-(2-iodophenyl)-2-pentyne (9). Deuterium labeling has confirmed that propargylation of 2 occurs ortho to the position originally occupied by the I(III). The addition of 2 equiv of 4a to 2 at -80-degrees-C results in 2 equiv each of 9, trimethylsilyl triflate (10), and tert-butyballene (11) and 1 equiv of hexamethyldisiloxane (12); in contrast, the addition of 2 equiv of 4b to 2 at -30-degrees-C results in 2 equiv each of 9 and tributylstannyl triflate (16). A mechanism that explains these product ratios is proposed. The reaction of 2-o,o'-d2 and 4b shows the negligible intramolecular kinetic isotope effect (0.99 +/- 0.01) expected for what is in effect a Claisen rearrangement. The addition of 2 to 2-butynyl (trimethylsilyl)methyl ether (20) affords the single product 21 resulting from anti addition and control of regiochemistry by the ether oxygen. Attempts to desilylate 21 to an allenyl triflate result in the regeneration of the propargyl ether 20.