(2R,5S)-2-Benzyl-5-[(tert-butoxycarbonyl)amino]-6-phenyl-(E)-3-hexen-1-ol | 155099-12-0

• 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: (2R,5S)-2-Benzyl-5-[(tert-butoxycarbonyl)amino]-6-phenyl-(E)-3-hexen-1-ol
• 英文别名: tert-butyl N-[(E,2S,5R)-5-benzyl-6-hydroxy-1-phenylhex-3-en-2-yl]carbamate
• CAS: 155099-12-0
• 化学式: C₂₄H₃₁NO₃
• 分子量: 381.515
• InChiKey: VDABJJRJYNDJJD-NPTPTYOFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.8
• 重原子数：
  28
• 可旋转键数：
  10
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  58.6
• 氢给体数：
  2
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (2R,5S)-2-Benzyl-5-[(tert-butoxycarbonyl)amino]-6-phenyl-(E)-3-hexen-1-ol 在 jones' reagent 、 四丁基氟化铵 、 间氯过氧苯甲酸 作用下， 以 四氢呋喃 、 乙醚 、 二氯甲烷 、 丙酮 为溶剂， 反应 40.5h， 生成 Methyl (4R,5S)-2-benzyl-5-<(tert-butoxycarbonyl)amino>-4-hydroxy-6-phenyl-(E)-2-hexenoate
  参考文献：
  名称：

  Stereoselective Epoxidation of Phe-Gly and Phe-Phe Vinyl Isosteres

  摘要：

  Novel Phe-Gly and Phe-Phe isosteres have been synthesized. Vinylic isosteres of Phe-Gly and Phe-Phe were prepared by facile Julia reactions, and the resulting stereoisomers were isolated and epoxidized (m-chloroperbenzoic acid). Observed stereoselectivities of epoxidation appear to emanate from a cooperative coordination of the incoming peracid by the carbamate group and the more weakly coordinating allylic ester function.

  DOI：

  10.1021/jo00084a037
• 作为产物：
  描述：

  ethoxycarbonyl (2S)-2-[(2-methylpropan-2-yl)oxycarbonylamino]-3-phenylpropanoate 在 sodium tetrahydroborate 、 disodium hydrogenphosphate 、 sodium amalgam 、 甲基锂 、 4-甲基苯磺酸吡啶 、 甲氧基二(2-甲基丙基)-铝 、 三乙胺 、 间氯过氧苯甲酸 作用下， 以 四氢呋喃 、 甲醇 、 乙醚 、 二氯甲烷 、 水 为溶剂， 反应 16.0h， 生成 (2R,5S)-2-Benzyl-5-[(tert-butoxycarbonyl)amino]-6-phenyl-(E)-3-hexen-1-ol
  参考文献：
  名称：

  立体控制的二肽反式链烯异构体的合成

  摘要：

  据报道，一般的合成路线是得到保护的二肽的反式链烯异构体。该序列允许以旋光形式和足够用于进一步生物学研究的量完全立体控制这些等位基因的制备。以这种方式制备的是TyrAla的烯烃等排体。PhePhe和LeuLe​​u。

  DOI：

  10.1016/s0040-4039(00)84457-3

文献信息

• Peracid dependent stereoselectivity and functional group contribution to the stereocontrol of epoxidation of (E)-alkene dipeptide isosteres
  作者：Daniel Wiktelius、Wei Berts、Annika Jenmalm Jensen、Joachim Gullbo、Stina Saitton、Ingeborg Csöregh、Kristina Luthman

  DOI：10.1016/j.tet.2006.01.095

  日期：2006.4

  on epoxidations with m-CPBA. The alkenes were synthesised in high yields with high E/Z-selectivities using either the Julia or Schlosser reactions. The formation of threo isomers was favoured in all epoxidation reactions except with CF3CO3H on substrates containing two allylic/homoallylic functional groups directing the peracid to opposite faces of the alkene. The switch to erythro selectivity observed

  将十二个Boc保护的苯丙氨酰基-苯丙氨酸和苯丙氨酰基-甘氨酸反式乙烯基等排物用单过氧邻苯二甲酸镁六水合物（MMPP）和三氟过氧乙酸进行环氧化，并将其结果与早期使用m- CPBA进行环氧化研究的结果进行了比较。使用Julia或Schlosser反应以高收率和高E / Z选择性合成烯烃。在所有环氧化反应中，苏式异构体的形成都受到促进，但在含有两个烯丙基/均烯丙基官能团的基质上将CF 3 CO 3 H导向过酸到烯烃的相对表面上除外。切换到建议使用CF 3 CO 3 H观察到的赤型选择性是通过过酸提供的氢键从配位基向烯丙基酯官能度发出的。其他过酸试剂似乎优先与烯丙基氨基甲酸酯官能团配位。还研究了各个官能团对立体偏好的贡献。
• Diastereoselective peracid epoxidation: Control of the face selectivity via functional group tuning and proper choice of epoxidation reagent
  作者：Annika Jenmalm Jensen、Kristina Luthman

  DOI：10.1016/s0040-4039(98)00393-1

  日期：1998.5

  Peracid epoxidation of 1a-f with 3-chloroperbenzoic acid (m-CPBA) and trifluoroperacetic acid (CF3CO3H) show different stereoselectivities. The olefins are substituted with two directing groups which are expected to direct the peracid to opposite faces of the alkene. Optimal face selectivities could be achieved by the proper choice of directing groups and epoxidation reagent.

  用3-氯过苯甲酸（m -CPBA）和三氟过氧乙酸（CF 3 CO 3 H）对1a-f进行过酸环氧化显示出不同的立体选择性。烯烃被两个引导基团取代，该两个引导基团预期将过酸引导至烯烃的相对表面。通过正确选择导向基团和环氧化试剂可以实现最佳的面部选择性。
• Stereoselective Epoxidation of Allylic Carbamates with m-Chloroperbenzoic Acid: The Role of Cooperative Coordination
  作者：Annika Jenmalm、Wei Berts、Kristina Luthman、Ingeborg Csoeregh、Uli Hacksell

  DOI：10.1021/jo00109a039

  日期：1995.2

  Stereoselective epoxidations of a series of allylic carbamate methyl esters 1a-d, homoallylic alcohols 1e-h, and acetates 1i-l have been performed using m-chloroperbenzoic acid (m-CPBA) as epoxidizing agent. Throughout, the formation of the three epoxides was favored. This selectivity is probably due to a directing effect of the carbamate group which forms a hydrogen bond to the peracid. However, the threo/erythro isomeric ratio is also dependent on steric interactions and on the possibility of cooperative coordination of the peracid to other suitably positioned functionalities such as allylic methyl ester, homoallylic alcohol, and acetate groups. The results of the present study indicate that the methyl ester is a weaker directing group than the carbamate. However the directing effect of the methyl ester is stronger than that of the homoallylic alcohol and acetate groups. A thermodynamic study of the epoxidation of two epimeric carbamate esters giving considerably different isomeric product ratios (9:1 compared to 2:1) indicates that the order in the transition state structure influences the isomeric ratios.