4-[(4-溴苯基)甲氧基]丁-2-烯-1-醇 | 108212-54-0

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 中文名称: 4-[(4-溴苯基)甲氧基]丁-2-烯-1-醇
• 英文名称: cis-4-(4-bromobenzyloxy)-but-2-en-1-ol
• 英文别名: (Z)-4-[(4-bromobenzyl)oxy]-2-buten-1-ol；(Z)-4-[(4-bromo)oxy]-2-buten-1-ol；(Z)-4-[(4-bromophenyl)methoxy]but-2-en-1-ol
• CAS: 108212-54-0
• 化学式: C₁₁H₁₃BrO₂
• 分子量: 257.127
• InChiKey: SRHBJWNLCAUJSU-UPHRSURJSA-N

物化性质

• 沸点：
  353.1±37.0 °C(Predicted)
• 密度：
  1.386±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  14
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.27
• 拓扑面积：
  29.5
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  4-[(4-溴苯基)甲氧基]丁-2-烯-1-醇 在 titanium(IV) isopropylate 、 叔丁基过氧化氢 、 4-二甲氨基吡啶 、 copper(l) iodide 、 L-(+)-酒石酸二异丙酯 、 三乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 16.42h， 生成 (2S,3R)-1-[(4-bromophenyl)methoxy]-3-[[tert-butyl(dimethyl)silyl]oxymethyl]pent-4-en-2-ol
  参考文献：
  名称：

  Synthesis of Methylene-Expanded Oxetanocin Isonucleosides in Both Enantiomeric Forms¹

  摘要：

  We report a novel route to isonucleosides of the 'methylene-expanded' oxetanocin class, in both the D-and L-enantiomeric forms, e.g., compounds L-(+)-2a, D-(-)-2a, and L-(-)-2b, beginning with the simple, known mono-p-bromobenzyl ether 3 of the very inexpensive 2-butene-1,4-diol. Sharpless asymmetric epoxidation of 3 gave either (-) or (+)-4 depending on the chirality of the tartrate used. The p-bromobenzyl ether was used since the epoxide product is crystalline and can be recrystallized to high optical purity. Opening of the epoxide with vinylmagnesium bromide gave the 1,3-diol 5, the primary alcohol of which was protected as the silyl ether 6. Treatment of 6 with iodonium bis(sym-collidine) perchlorate afforded the desired 5-(iodomethyl)tetrahydrofuran-3-ol 8 with loss of the bromobenzyl cation in the key step in the synthetic scheme. This iodide 8 was then converted into the bis(silyloxy)-protected alcohol 15 by acetylation to give the acetate 10, displacement of iodide with acetate, hydrolysis, and selective protection of the primary alcohols. The alcohol 6 could also be converted into 15 via initial acetylation and then iodocyclization to give 10. The diol 5 could also be converted into 15 by a similar route involving bis-acetylation and iodocyclization followed by functional group transformations. The tosylate of 15 was displaced with the anion of adenine or thymidine to give, alter final desilylation, the desired isonucleosides-the D-adenosine analogue (-)-2a and the L-adenosine and thymidine analogues (+)-2a and(-)-2b. All of the stereochemistry of the final products is derived from the first step of the synthesis, namely, the Sharpless asymmetric epoxidation of 3. The biological activity of the new compounds L-(+)-2a and L-(-)-2b against HIV was determined in the anti-HIV drug-testing system of the National Cancer Institute. The adenosine analogue L-(+)-2a was inactive in this screen, while the thymidine analogue L-(-)-2b showed moderate anti-HIV activity (IC50 > 2 x 10(-4) M, EC50 = 8 x 10(-7) M, TI50 > 250).

  DOI：

  10.1021/jo971890c
• 作为产物：
  描述：

  顺式-1,2-二羟甲基乙烯 、 对溴溴苄 在 四丁基碘化铵 、 sodium hydride 作用下， 以 四氢呋喃 为溶剂， 反应 15.0h， 以88%的产率得到4-[(4-溴苯基)甲氧基]丁-2-烯-1-醇
  参考文献：
  名称：

  Rhizoxin D的全合成，Rhizoxin D是一种来自真菌Rhizopus chinensis的有效抗有丝分裂剂。

  摘要：

  根霉菌素D（2）由分别代表C3-C9，C10-C13，C14-C19和C20-C27的四个亚基A，B，C和D合成。亚基A是通过碘代乙缩醛21的环化制备的，该碘代乙缩醛21通过在（Z）-α，β-不饱和酯的β碳上立体选择性地添加衍生自21的脱卤基团而将C5的构型设定为2。乙醛29从苯硫缩醛24中获得，并在代表Wittig的Wittig反应中与代表亚基B的磷烷30缩合。该酯被转化为醛33，以准备与亚基C偶联。由炔丙醇经六步获得甲基酮形式的甲基酮55。33的醇醛缩醛反应与用（+）-DIPCl制备的55的烯醇缩醛反应，得到具有（13S）-构型的期望的β-羟基酮56，与（13R）-非对映异构体的比率为17-20：1。还原成抗二醇57并作为TIPS醚58进行选择性保护后，将C15羟基酯化得到膦酸酯59。衍生自δ-内酯60的醛62的分子内Wadsworth-Emmons反应提供了大内酯63，该大内酯63在

  DOI：

  10.1021/jo020537q

文献信息

• Diastereoface differentiation in addition of lithium enolates to chiral α,β-epoxyaldehydes
  作者：Jean-Marc Escudier、Michel Baltas、Liliane Gorrichon

  DOI：10.1016/s0040-4020(01)82375-9

  日期：1993.6

  aldolisation reaction of lithium ester enolates with chiral α,β-epoxyaldehydes 2a–2f has been investigated. The reaction proceeds with diastereofacial preference in favour of the anti isomer (anti:syn ≈ 4:1) and can be greatly enhanced in the case of cis α,β-epoxy-aldehydes 2a–2c by a synergic effect of temperature and enolate excess (anti:syn 13:1). The Felkin-Ahn model can explain the results obtained

  已经研究了酯酸锂与手性α，β-环氧醛2a–2f的醛醇缩合反应。反应以非对映体优先进行，有利于抗异构体（anti：syn≈4：1），在顺式α，β-环氧-醛2a–2c的情况下，温度和烯醇过量的协同作用可以大大增强反应（反：syn 13：1）。Felkin-Ahn模型可以解释在不对称感应下获得的结果。
• Process for preparation of chiral 3-amino-pyrrolidine and analogous
  申请人：Abbott Laboratories

  公开号：US05703244A1

  公开（公告）日：1997-12-30

  A process for the preparation of chiral 3-aminopyrrolidine and analogous bicyclic derivatives from dihydroxy olefins by treatment with titanium isopropoxide, an optically active tartrate ester and tert-butyl hydroperoxide, followed by subsequent alkylation of the intermediate with an alkyl or alkenyl magnesium halide, then pyrrolidine ring formation by condensation with an arylmethylamine, subsequent chiral replacement of a ring hydroxyl group with an amino group with further protection thereof, optional additional substitution closing of the second ring, and hydrogenolysis to remove a ring-nitrogen protecting group.

  通过与异丙氧基钛、光学活性酒石酸酯和叔丁基过氧化氢处理二羟基烯烃，然后通过与烷基或烯基镁卤化物进行中间体烷基化，随后通过与芳基甲基胺缩合形成吡咯烷环，随后通过将环羟基替换为氨基并进一步保护，可选地进行第二环的附加取代封闭，最后通过氢解去除环氮保护基，制备手性3-氨基吡咯烷及类似的双环衍生物的制备方法。
• Facile preparation of (2R,3S)- and (2S,3R)-3-[[(4-bromobenzyl)oxy]methyl]oxirane-2-methanol via asymmetric epoxidation
  作者：J. Michael Chong、Susanna Wong

  DOI：10.1021/jo00388a050

  日期：1987.6
• CHONG J. M.; WONG S., J. ORG. CHEM., 52,(1987) N 12, 2596-2598
  作者：CHONG J. M.、 WONG S.

  DOI：——

  日期：——
• US5703244A
  申请人：——

  公开号：US5703244A

  公开（公告）日：1997-12-30