(+)-S-1,1-dibromo-6-(tert-butyldimethylsilyloxy)-2-(N,N-dibenzylamino)-1-hexene | 205068-05-9

• 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: (+)-S-1,1-dibromo-6-(tert-butyldimethylsilyloxy)-2-(N,N-dibenzylamino)-1-hexene
• 英文别名: (3S)-N,N-dibenzyl-1,1-dibromo-6-[tert-butyl(dimethyl)silyl]oxyhex-1-en-3-amine
• CAS: 205068-05-9
• 化学式: C₂₆H₃₇Br₂NOSi
• 分子量: 567.479
• InChiKey: IRRAOCPTXWHONX-DEOSSOPVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.49
• 重原子数：
  31.0
• 可旋转键数：
  11.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.46
• 拓扑面积：
  12.47
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  (+)-S-1,1-dibromo-6-(tert-butyldimethylsilyloxy)-2-(N,N-dibenzylamino)-1-hexene 在 bis-triphenylphosphine-palladium(II) chloride 、 copper(l) iodide 、 正丁基锂 、 四丁基氟化铵 、 仲丁基锂 、 sodium hydride 、 三乙胺 、 鹰爪豆碱 作用下， 以 四氢呋喃 、 乙醚 为溶剂， 反应 24.0h， 生成 (-)-[1S,3S,2(1E)]-2-benzylidene-3-(N,N-dibenzylamino)-6-phenyl-5-hexynyl 2,2,4,4-tetramethyl-1,3-oxazolidine-3-carboxylate
  参考文献：
  名称：

  (−)-Sparteine-Mediated Stereoselective Intramolecular Carbolithiation of 4-Substituted 5-Hexynyl Carbamates. Synthesis of Enantiopure 1,3-Difunctionalized Alkylidene Cyclopentanes

  摘要：

  The stereoselective carbolithiation of alkynes with external chiral induction has been achieved for the first time by fusing the concepts of the asymmetric deprotonation (A) with s-BuLi/(-)-sparteine (s-BuLi/1) and the intramolecular carbolithiation (B). Several 4-functionalized 5-hexynyl carbamates with different terminal substituents have been prepared and efficiently cyclized providing enantiopure highly substituted alkylidene cyclopentanes. The presence of a sterically demanding substituent in the propargylic position is the essential feature of these cyclizations in order to suppress the abstraction of the remaining propargylic proton. Furthermore, in dependence on the terminal substituent, the 6-phenyl-substituted precursors undergo an intramolecular carbolithiation whereas for the 6-trimethylsilyl-substituted alkynes a sub sequent migration of the O-carbamoyl group onto the vinylic carbanionic center follows.

  DOI：

  10.1021/jo991095u
• 作为产物：
  描述：

  (S)-2-(N,N-dibenzylamino)-5-(tert-butyldimethylsilyloxy)pentan-1-ol 在 草酰氯 、 二甲基亚砜 、 三乙胺 、 三苯基膦 作用下， 以 二氯甲烷 为溶剂， 反应 1.0h， 生成 (+)-S-1,1-dibromo-6-(tert-butyldimethylsilyloxy)-2-(N,N-dibenzylamino)-1-hexene
  参考文献：
  名称：

  (−)-Sparteine-Mediated Stereoselective Intramolecular Carbolithiation of 4-Substituted 5-Hexynyl Carbamates. Synthesis of Enantiopure 1,3-Difunctionalized Alkylidene Cyclopentanes

  摘要：

  The stereoselective carbolithiation of alkynes with external chiral induction has been achieved for the first time by fusing the concepts of the asymmetric deprotonation (A) with s-BuLi/(-)-sparteine (s-BuLi/1) and the intramolecular carbolithiation (B). Several 4-functionalized 5-hexynyl carbamates with different terminal substituents have been prepared and efficiently cyclized providing enantiopure highly substituted alkylidene cyclopentanes. The presence of a sterically demanding substituent in the propargylic position is the essential feature of these cyclizations in order to suppress the abstraction of the remaining propargylic proton. Furthermore, in dependence on the terminal substituent, the 6-phenyl-substituted precursors undergo an intramolecular carbolithiation whereas for the 6-trimethylsilyl-substituted alkynes a sub sequent migration of the O-carbamoyl group onto the vinylic carbanionic center follows.

  DOI：

  10.1021/jo991095u