methyl (2R,5S)-2-benzyl-5-t-butoxycarbonylamino-6-phenyl-E-3-hexenoate | 137278-30-9

• 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: methyl (2R,5S)-2-benzyl-5-t-butoxycarbonylamino-6-phenyl-E-3-hexenoate
• 英文别名: Methyl (2R,5S)-2-Benzyl-5-[(tert-butoxycarbonyl)amino]-6-phenyl-(E)-3-hexenoate；trans-(2R,5S)-Methyl 2-Benzyl-5-(t-butyloxycarbonylamino)-6-phenyl-3-hexenoate；methyl (E,2R,5S)-2-benzyl-5-[(2-methylpropan-2-yl)oxycarbonylamino]-6-phenylhex-3-enoate
• CAS: 137278-30-9
• 化学式: C₂₅H₃₁NO₄
• 分子量: 409.525
• InChiKey: IYZQZUDTHASFOG-BJPOSOMNSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.2
• 重原子数：
  30
• 可旋转键数：
  11
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  64.6
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  methyl (2R,5S)-2-benzyl-5-t-butoxycarbonylamino-6-phenyl-E-3-hexenoate 在 四丁基氟化铵 、 间氯过氧苯甲酸 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 40.0h， 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：

  2-Benzyl-3-<(tert-butyldimethylsilyl)oxy>-1-propanol 在 jones' reagent 、 草酰氯 、 二甲基亚砜 、 N,N-二异丙基乙胺 作用下， 以 乙醚 、 二氯甲烷 、 丙酮 为溶剂， 反应 0.5h， 生成 methyl (2R,5S)-2-benzyl-5-t-butoxycarbonylamino-6-phenyl-E-3-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

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。
• <i>E-</i>Olefin Dipeptide Isostere Incorporation into a Polypeptide Backbone Enables Hydrogen Bond Perturbation:  Probing the Requirements for Alzheimer's Amyloidogenesis
  作者：Yanwen Fu、Jan Bieschke、Jeffery W. Kelly

  DOI：10.1021/ja0551382

  日期：2005.11.1

  Herein, we report a stereospecific E-olefin dipeptide isostere synthesis that can be used to make gram quantities of the Phe-Phe isostere desired for eliminating a specific backbone H-bond donor and acceptor in the Alzheimer's disease related Abeta peptide. The Phe19-Phe20 E-olefin analogue of Abeta(1-40) was prepared by solid-phase peptide synthesis and was subjected to amyloidogenesis conditions

  在此，我们报告了一种立体特异性 E-烯烃二肽等排体合成，可用于制造克数量的 Phe-Phe 等排体，用于消除阿尔茨海默病相关 Abeta 肽中的特定骨架 H 键供体和受体。Abeta(1-40) 的 Phe19-Phe20 E-烯烃类似物是通过固相肽合成制备的，并受到淀粉样蛋白生成条件的影响。这种类似物可以聚集成球形形态，但不会像全酰胺序列那样继续形成原原纤维或原纤维，从而深入了解淀粉样变性的结构要求。
• Process for the preparation of a dipeptide isostere
  申请人：Abbott Laboratories

  公开号：US05130468A1

  公开（公告）日：1992-07-14

  A process and intermediates useful for the preparation of (E)-alkene dipeptide isosteres are disclosed.

  本发明揭示了一种用于制备(E)-烯烃二肽同分异构体的过程和中间体。
• “Higher order” zinc cuprates involving lithium chloride: Synthesis of (E)-alkene dipeptide isosteres free from reductive elimination products
  作者：Toshiro Ibuka、Hidenori Yoshizawa、Hiromu Habashita、Nobutaka Fujii、Yukiyasu Chounan、Miwa Tanaka、Yoshinori Yamamoto

  DOI：10.1016/0040-4039(92)80024-e

  日期：1992.6

  The “higher order” organozinc cuprates, R2Cu(CN)(ZnCl)2·2Mg(X)Cl·nLiCl, derived from admixture of LiCl (1∼2 equiv.), ZnCl2 (1 equiv.), RMgX (1 equiv.), and CuCN (0.5 equiv.) in a mixed solvent of THF and Et2O exhibit high diastereoselection of up to > 99: 1 in the synthesis of (E)-alkene dipeptide isosteres from γ-mesyloxy-α,β-unsaturated esters. Addition of lithium chloride is essential for the preparation

  “高阶”有机锌铜酸盐R 2 Cu（CN）（ZnCl）2 ·2Mg（X）Cl·nLiCl，由LiCl（1〜2当量），ZnCl 2（1当量），RMgX（ 1当量），而在THF和Et 2 O的混合溶剂中的CuCN（0.5当量）在从γ-甲磺酰氧基-α合成（E）-烯烃二肽等排体中表现出高达> 99：1的高非对映选择性， β-不饱和酯。添加氯化锂对于制备澄清的试剂溶液至关重要。
• 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。