(E)-(2R,3S)-1,2-O-isopropylidene-3-benzyloxy-4-methyl-hex-4-ene-1,2-diol | 167777-52-8

• 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: (E)-(2R,3S)-1,2-O-isopropylidene-3-benzyloxy-4-methyl-hex-4-ene-1,2-diol
• 英文别名: (4R)-2,2-dimethyl-4-[(E,1S)-2-methyl-1-phenylmethoxybut-2-enyl]-1,3-dioxolane
• CAS: 167777-52-8
• 化学式: C₁₇H₂₄O₃
• 分子量: 276.376
• InChiKey: MEUBMSHFEUADDI-PLAYSVDASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  20
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.53
• 拓扑面积：
  27.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (E)-(2R,3S)-1,2-O-isopropylidene-3-benzyloxy-4-methyl-hex-4-ene-1,2-diol 在 lead(IV) acetate 、 三氟乙酸 作用下， 以 甲醇 、 二氯甲烷 、 水 为溶剂， 反应 48.25h， 生成 (E)-(S)-2-Benzyloxy-3-methyl-pent-3-enal
  参考文献：
  名称：

  Mulzer, Johann; Bilow, Joern; Wille, Gregor, Advanced Synthesis and Catalysis, 2000, vol. 342, # 8, p. 773 - 778

  摘要：

  DOI：
• 作为产物：
  描述：

  (R)-4-((1S,2R)-1-benzyloxy-2-methylbut-3-enyl)-2,2-dimethyl-[1,3]dioxolane 在 sodium hydride 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 4.0h， 生成 (E)-(2R,3S)-1,2-O-isopropylidene-3-benzyloxy-4-methyl-hex-4-ene-1,2-diol
  参考文献：
  名称：

  A mechanistically unusual base induced [1,3]-H-shift in homoallylic ethers

  摘要：

  Upon treatment with NaH in DMF the homoallylic ethers 1a-g and the amine 1h undergo a rearrangement into the trisubstituted (Epsilon)- olefins 2a-h. Experiments with isotopically labelled forms of 1a and 1b show that the [1,3]-shift is cleanly intramolecular and proceeds predominantly in the suprafacial mode. (C) 1997 Elsevier Science Ltd.

  DOI：

  10.1016/s0040-4039(97)01223-9

文献信息

• Synthesis of Optically Active β,γ-Unsaturated α-Amino Acids and of α,β-Unsaturated γ-Amino Acids. SN2- vs. SN2’-Dichotomy of the Mitsunobu Amination of Allylic Alcohols
  作者：Johann Mulzer、Günther Funk

  DOI：10.1055/s-1995-3847

  日期：1995.1

  Novel and efficient syntheses (6-9 steps, overall yields 10-30%) are described for optically pure β,γ-unsaturated α-amino acids and α,β-unsaturated γ-amino acids, starting from (R)-isopropylidene glyceraldehyde and ethyl (S)-lactate, respectively. The key step is the Mitsunobu reaction of chiral secondary allylic alcohols with phthalimide as the nucleophile, where α,γ allylic transpositions are observed for the first time. The structure-α,γ-ratio-relationship is studied and also the stereochemistry of the allylic transposition. The α-substitution proceeds via clean SN2 inversion, whereas the γ-substitution corresponds to an (E)-anti attack of the nucleophilic with varying stereoselectivities.

  本文描述了从（R）-异丙叉甘油醛和乙基（S）-乳酸分别合成光学纯的β,γ-不饱和α-氨基酸和α,β-不饱和γ-氨基酸的新颖且高效的方法（总步骤为6-9步，总收率为10-30%）。关键步骤是手性仲烯丙醇与酞酰亚胺作为亲核试剂的 Mitsunobu 反应，首次观察到α,γ 烯丙基重排现象。研究了结构-α,γ 比例关系以及烯丙基重排的立体化学。α-取代过程通过干净的 SN2 反转进行，而γ-取代对应于亲核试剂的（E）-反向攻击，具有不同的立体选择性。
• Mulzer, Johann; Bilow, Joern; Wille, Gregor, Advanced Synthesis and Catalysis, 2000, vol. 342, # 8, p. 773 - 778
  作者：Mulzer, Johann、Bilow, Joern、Wille, Gregor

  DOI：——

  日期：——
• A mechanistically unusual base induced [1,3]-H-shift in homoallylic ethers
  作者：Johann Mulzer、Gregor Wille、Jörn Bilow、Duilio Arigoni、Bruno Martinoni、Konrad Roten

  DOI：10.1016/s0040-4039(97)01223-9

  日期：1997.8

  Upon treatment with NaH in DMF the homoallylic ethers 1a-g and the amine 1h undergo a rearrangement into the trisubstituted (Epsilon)- olefins 2a-h. Experiments with isotopically labelled forms of 1a and 1b show that the [1,3]-shift is cleanly intramolecular and proceeds predominantly in the suprafacial mode. (C) 1997 Elsevier Science Ltd.