(E)-(3R,4R)-6-iodo-4-methyl-5-hexen-3-ol | 216493-79-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (E)-(3R,4R)-6-iodo-4-methyl-5-hexen-3-ol
• 英文别名: (E,3R,4R)-6-iodo-4-methylhex-5-en-3-ol
• CAS: 216493-79-7
• 化学式: C₇H₁₃IO
• 分子量: 240.084
• InChiKey: WOLQKGIJLDTKMX-XIMOZBJHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  9
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (E)-(3R,4R)-6-iodo-4-methyl-5-hexen-3-ol 在 4-二甲氨基吡啶 、 2,4,6-三氯苯甲酰氯 、 氢氟酸 、 三乙胺 作用下， 以 乙腈 为溶剂， 反应 26.0h， 生成 [(E,3R,4R)-6-iodo-4-methylhex-5-en-3-yl] (2R,3S,4S,6R)-7-hydroxy-3-[(4-methoxyphenyl)methoxy]-2,4,6-trimethylheptanoate
  参考文献：
  名称：

  Total Synthesis of 10-Deoxymethynolide, the Aglycon of the Macrolide Antibiotic 10-Deoxymethymycin

  摘要：

  A short and efficient total synthesis of 10-deoxymethynolide (2c), the aglycon of 10-deoxymethymycin (1c), has been accomplished in 16 steps and 12% overall yield from (S)-3-O-p-toluenesulfonyl-3-hydroxy-2-methylpropanal (15c). The synthesis features an expeditious preparation of (+)-5a, a synthetic equivalent of the Prelog-Djerassi lactonic acid, and the construction of a 12-membered lactone through an intramolecular Nozaki-Hiyama-Kishi coupling reaction.

  DOI：

  10.1021/jo9809433
• 作为产物：
  描述：

  (2S,3R)-3-(tert-butyldimethylsilyloxy)-N-methoxy-N,2-dimethylpentanamide 在 chromium dichloride 、 氢氟酸 、 二异丁基氢化铝 作用下， 以 四氢呋喃 、 甲苯 、 乙腈 为溶剂， 反应 7.0h， 生成 (E)-(3R,4R)-6-iodo-4-methyl-5-hexen-3-ol
  参考文献：
  名称：

  Total Synthesis of 10-Deoxymethynolide, the Aglycon of the Macrolide Antibiotic 10-Deoxymethymycin

  摘要：

  A short and efficient total synthesis of 10-deoxymethynolide (2c), the aglycon of 10-deoxymethymycin (1c), has been accomplished in 16 steps and 12% overall yield from (S)-3-O-p-toluenesulfonyl-3-hydroxy-2-methylpropanal (15c). The synthesis features an expeditious preparation of (+)-5a, a synthetic equivalent of the Prelog-Djerassi lactonic acid, and the construction of a 12-membered lactone through an intramolecular Nozaki-Hiyama-Kishi coupling reaction.

  DOI：

  10.1021/jo9809433

文献信息

• Formal Total Synthesis of the Polyketide Macrolactone Narbonolide
  作者：Lakshmanan Venkatraman、Courtney C. Aldrich、David H. Sherman、Robert A. Fecik

  DOI：10.1021/jo050924a

  日期：2005.9.1

  An improved synthesis of (3S)-3-dihydronarbonolide is reported that constitutes a formal total synthesis of the 14-membered macrolactone antibiotic narbonolide. The key step was an intramolecular Nozaki−Hiyama−Kishi coupling to accomplish macrocyclization in improved yield. The high level of convergence will also allow us to rapidly synthesize narbonolide analogues for the study of enzymes in the pikromycin

  据报道，改进的（3S）-3-二氢那波内酯的合成构成了十四元大内酯类抗生素那波内酯的正式全合成。关键步骤是分子内的Nozaki-Hiyama-Kishi偶联，以提高产量实现大环化。高水平的融合也将使我们能够快速合成narbonolide类似物，以研究吡咯霉素生物合成途径中的酶。
• Studies directed towards the total synthesis of narbonolide: stereoselective synthesis of the C1–C15 chain
  作者：Jhillu S. Yadav、Aala Kavita、Kovvuri V. Raghavendra Rao、Debendra K. Mohapatra

  DOI：10.1016/j.tetlet.2013.04.023

  日期：2013.6

  A stereoselective synthesis of the C1–C15 chain of narbonolide, a 14-membered macrolactone belonging to the pikromycin family of antibiotics is described. The key steps involved in this synthesis are desymmetrization of bicyclic olefin with Brown’s asymmetric hydroboration, Evans aldol reaction, Takai olefination and Yamaguchi esterification to yield the corresponding ester.

  描述了那波内酯C1–C15链的立体选择性合成，那波内酯是一种属于吡科霉素抗生素家族的14元大内酯。合成中涉及的关键步骤是用布朗氏不对称硼氢化反应对双环烯烃进行不对称化，Evans aldol反应，Takai烯烃化反应和Yam​​aguchi酯化反应以生成相应的酯。
• Total Synthesis of Narbonolide and Biotransformation to Pikromycin
  作者：Lakshmanan Venkatraman、Christine E. Salomon、David H. Sherman、Robert A. Fecik

  DOI：10.1021/jo062047u

  日期：2006.12.1

  improved total synthesis of narbonolide and its biotransformation to pikromycin is reported. This total synthesis utilized an intramolecular Nozaki−Hiyama−Kishi coupling that significantly improved macrocyclization yields (90−96%) and allowed for differentiation of the C3- and C5-oxidation states. A pikAI deletion mutant of Streptomyces venezuelae was used to biotransform synthetic narbonolide to pikromycin

  据报道，纳波内酯的总合成得到改善，并且可以生物转化为吡咯霉素。该总合成利用了分子内的Nozaki-Hiyama-Kishi偶联，该偶联显着提高了大环化率（90-96％），并允许C3-和C5-氧化态的区分。委内瑞拉链霉菌的一个pikAI缺失突变体通过体内糖基化和氧化作用，将合成的narbonolide转化为吡珠霉素。合成化学和工程生物转化的这种结合对于合成具有生物学意义的新型大环内酯类似物具有广阔的前景。