trans-1-(benzyloxy)-4,4-dimethyl-2,3-epoxypentane

• 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: trans-1-(benzyloxy)-4,4-dimethyl-2,3-epoxypentane
• 英文别名: (2S,3S)-2-tert-butyl-3-(phenylmethoxymethyl)oxirane
• 化学式: C₁₄H₂₀O₂
• 分子量: 220.312
• InChiKey: LUGYJUBNMBLWOI-QWHCGFSZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  16
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  21.8
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  trans-1-(benzyloxy)-4,4-dimethyl-2,3-epoxypentane 在 Cr(tBuN)Cl₃(1,2-dimethoxyethane) 作用下， 以 二氯甲烷 为溶剂， 反应 24.0h， 生成 (2R,3S)-1-Benzyloxy-2-chloro-4,4-dimethyl-pentan-3-ol 、 (2R,3S)-1-Benzyloxy-3-chloro-4,4-dimethyl-pentan-2-ol
  参考文献：
  名称：

  Leung, Wa-Hung; Wong, Terry K. T.; Tran, Jeff C. H., Synlett, 2000, # 5, p. 677 - 679

  摘要：

  DOI：
• 作为产物：
  描述：

  ethyl (E)-4,4-dimethyl-2-pentenoate 在 4 A molecular sieve titanium(IV) isopropylate 、 叔丁基过氧化氢 、 L-(+)-酒石酸二异丙酯 、 sodium hydride 、 二异丁基氢化铝 作用下， 以 异辛烷 、 乙醚 、 正己烷 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 11.0h， 生成 trans-1-(benzyloxy)-4,4-dimethyl-2,3-epoxypentane
  参考文献：
  名称：

  包含大量烷基的模块氨基醇配体作为醛除Et2Zn的手性控制剂：设计原理的说明。

  摘要：

  一个新的对映体纯的（1S，2R）-1-烷基-2-（二烷基氨基）-3-（R-氧基）-1-丙醇在其上含有非常庞大的烷基取代基（叔丁基或1-金刚烷基）烃链是由相应的对映体纯环氧醇合成的，该醇由催化的Sharpless环氧化作用产生，通过伯羟基的保护和随后环仲胺的环选择性开环（C-2攻击）来实现。已经研究了这些氨基醇作为二乙基锌催化对映选择性加成至苯甲醛的配体的性能，记录的对映选择性为92-96％。最佳性能的配体，那些带有庞大的R-氧基的配体，在将Et（2）Zn添加到一个代表性的醛家族中时，也显示了便利的活性和选择性。

  DOI：

  10.1021/jo034007l

文献信息

• Regiochemical control of the ring opening of 1,2-epoxides by means of chelating processes. 5. Synthesis and reactions of some 2,3-epoxy-1-alkanol derivatives
  作者：Marco Chini、Paolo Crotti、Lee A. Flippin、Cristina Gardelli、Elena Giovani、Franco Macchia、Mauro Pineschi

  DOI：10.1021/jo00057a040

  日期：1993.2

  In order to study the effect of a remote polar functionality on the regiochemistry of the ring opening of aliphatic epoxides, the synthesis and some nucleophilic additions (methanolysis, azidolysis, and aminolysis) of suitable 2,3-epoxy-1-alkanol derivatives (epoxides trans-1a-d and cis-2) were carried out. The C-3 selectivity commonly observed when nonchelating ring opening conditions are used is lower than when the epoxides are allowed to react in the presence of metal ions (Li+, Mg2+, Zn2+) due to the probable intervention of bidentate-chelated intermediates in the latter case, and in some instances an almost complete C-3 regioselection is obtained. Under identical conditions involving chelation control, trans epoxide la shows higher C-3 selectivity than cis isomer 2. A free hydroxyl functionality is not necessary in order to observe chelation-controlled regioselectivity in the epoxides that we examined.
• Regiochemical control of the ring opening of 1,2-epoxides by means of chelating processes. Part 18: Regioselectivity of the opening reactions with MeOH of 1-(benzyloxy)-2,3- and -3,4-epoxyalkanes under condensed and gas phase operating conditions
  作者：Paolo Crotti、Gabriele Renzi、Graziella Roselli、Valeria Di Bussolo、Laura Lucarelli、Maria Rosaria Romano

  DOI：10.1016/j.tet.2005.05.040

  日期：2005.8

  The regiochemical behavior of a series of aliphatic open chain epoxides bearing a heterofunctionality in an allylic or homoallylic relationship has been examined in the opening reaction with MeOH under both condensed and gas phase operating conditions. The results indicate that the proton (actually D+) possesses in the gas phase intrinsic chelating properties which are even superior than those of Li (+) in the condensed phase. (c) 2005 Elsevier Ltd. All rights reserved.