((1S,6S)-6-(iodomethyl)cyclohex-3-enyl)methanol | 956005-67-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: ((1S,6S)-6-(iodomethyl)cyclohex-3-enyl)methanol
• 英文别名: ((1S,6S)-6(iodomethyl)cyclohex-3-enyl)methanol；[(1S,6S)-6-(iodomethyl)cyclohex-3-en-1-yl]methanol
• CAS: 956005-67-7
• 化学式: C₈H₁₃IO
• 分子量: 252.095
• InChiKey: DVFRGYCWUFXJNM-HTQZYQBOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  10
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.75
• 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：

  ((1S,6S)-6-(iodomethyl)cyclohex-3-enyl)methanol 、 (S)-3-(2'-chloro-1'-ethylidene)amino-4-phenylmethyl-2-oxazolidinone 在 indium(III) chloride 、 羰基镁 、 三乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 1.34h， 以30%的产率得到(S)-4-benzyl-3-((S)-3-chloro-1-((1R,6S)-6-(hydroxymethyl)cyclohex-3-enyl)propan-2-ylamino)oxazolidin-2-one
  参考文献：
  名称：

  Quinine Synthesis Studies:  A Radical−Ionic Annulation via Mn-Mediated Addition to Chiral N-Acylhydrazones

  摘要：

  A radical-ionic annulation approach to functionalized perhydroisoquinolines involving Mn-mediated coupling of alkyl iodides and chiral N-acylhydrazones was achieved using only 1.25 equiv of the alkyl iodide. Application of this reaction to alkene-containing substrates en route to quinine offered modest yields, decreasing on scaleup. Control experiments revealed that the alkene interfered with the coupling reaction. A revised approach involving prior oxidation of the alkene offered 93% yield in the Mn-mediated coupling, with the adduct obtained as a single diastereomer.

  DOI：

  10.1021/ol7017938
• 作为产物：
  描述：

  ((1S,6S)-6-((tert-butyldimethylsilyloxy)methyl)cyclohex-3-enyl)methanol 在 咪唑 、 camphor-10-sulfonic acid 、 碘 、 三苯基膦 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 4.42h， 生成 ((1S,6S)-6-(iodomethyl)cyclohex-3-enyl)methanol
  参考文献：
  名称：

  Quinine Synthesis Studies:  A Radical−Ionic Annulation via Mn-Mediated Addition to Chiral N-Acylhydrazones

  摘要：

  A radical-ionic annulation approach to functionalized perhydroisoquinolines involving Mn-mediated coupling of alkyl iodides and chiral N-acylhydrazones was achieved using only 1.25 equiv of the alkyl iodide. Application of this reaction to alkene-containing substrates en route to quinine offered modest yields, decreasing on scaleup. Control experiments revealed that the alkene interfered with the coupling reaction. A revised approach involving prior oxidation of the alkene offered 93% yield in the Mn-mediated coupling, with the adduct obtained as a single diastereomer.

  DOI：

  10.1021/ol7017938

文献信息

• Scope of Stereoselective Mn-Mediated Radical Addition to Chiral Hydrazones and Application in a Formal Synthesis of Quinine
  作者：Gregory K. Friestad、An Ji、Jonas Baltrusaitis、Chandra Sekhar Korapala、Jun Qin

  DOI：10.1021/jo2026349

  日期：2012.4.6

  favored an undesired azabicyclo[3.2.1]octane ring system, an outcome that was found to be consistent with transition state calculations at the B3LYP/6-31G(d) level. Group differentiation at an earlier stage enabled an alternative regioconvergent pathway; this furnished the desired azabicyclo[2.2.2]octane ring system and afforded quincorine (21b), completing a formal synthesis of quinine.

  立体控制的锰介导的烷基碘与手性N-酰基腙的加成能够在手性胺的立体中心构建战略性 C-C 键。将此策略应用于奎宁提出了互补的合成方法，使用多功能烷基碘6a - d作为自由基前体，或使用多功能手性N-酰基腙26a - d作为自由基受体，构建连接在含氮立体中心的 C-C 键。这些被包括在锰介导的各种烷基碘与一系列手性N 的自由基加成中-酰基腙自由基受体，导致发现吡啶和烯烃官能团不相容。在修改后的策略中，在 Mn 介导的自由基加成6d到手性N-酰基腙22b过程中避免了这些功能，它在奎宁的手性胺碳上产生了一个具有完全立体化学控制的关键 C-C 键。随后的阐述包括两个连续环化以完成氮杂双环 [2.2.2] 辛烷环系统。第二次环化期间两个 2-碘乙基之间的基团选择性有利于不希望的氮杂双环 [3.2.1] 辛烷环系统，发现这一结果与 B3LYP/6-31G(d) 水平的过渡态计算一致。早期的群体分化启用了