(R)-6-(iodomethyl)-6-(4-methoxyphenyl)tetrahydro-2H-pyran-2-one | 1370729-72-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: (R)-6-(iodomethyl)-6-(4-methoxyphenyl)tetrahydro-2H-pyran-2-one
• 英文别名: (6R)-6-(iodomethyl)-6-(4-methoxyphenyl)oxan-2-one
• CAS: 1370729-72-8
• 化学式: C₁₃H₁₅IO₃
• 分子量: 346.165
• InChiKey: NROMDHXSDQJYSL-ZDUSSCGKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3
• 重原子数：
  17
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.46
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  5-(4-methoxyphenyl)hex-5-enoic acid methyl ester 在 N-碘代丁二酰亚胺 、 lithium hydroxide monohydrate 、 3-((3,5-bis(trifluoromethyl)phenyl)amino)-4-(((1R,2R)-2-(dipentylamino)cyclohexyl)amino)cyclobut-3-ene-1,2-dione 、 水 、 碘 作用下， 以 四氢呋喃 、 二氯甲烷 、 丙酮 为溶剂， 反应 24.0h， 生成 (S)-6-(iodomethyl)-6-(4-methoxyphenyl)tetrahydro-2H-pyran-2-one 、 (R)-6-(iodomethyl)-6-(4-methoxyphenyl)tetrahydro-2H-pyran-2-one
  参考文献：
  名称：

  Asymmetric Iodolactonization Utilizing Chiral Squaramides

  摘要：

  Asymmetric iodolactonization of gamma- and delta-unsaturated carboxylic acids has been explored in the presence of six different chiral organocatalysts 5-8. The catalyst 6b was found to facilitate the cyclization of 5-arylhex-5-enoic acids 1 to the corresponding iodolactones 2 with up to 96% ee. By this protocol, unsaturated carboxylic acids are converted enantioselectively to synthetically useful delta-lactones in high yields using commercially available NIS. Apparently, both hydrogen bonding and aryl/aryl interactions are important for efficient stereodifferentiation.

  DOI：

  10.1021/ol302798g

文献信息

• Achiral Counterion Control of Enantioselectivity in a Brønsted Acid-Catalyzed Iodolactonization
  作者：Mark C. Dobish、Jeffrey N. Johnston

  DOI：10.1021/ja301858r

  日期：2012.4.11

  Highly enantioselective halolactonizations have been developed that employ a chiral proton catalyst-N-iodosuccinimide (NIS) reagent system in which the Brønsted acid is used at catalyst loadings as low as 1 mol %. An approach that modulates the achiral counterion (equimolar to the neutral chiral ligand-proton complex present at low catalyst loadings) to optimize the enantioselection is documented for

  已经开发出高度对映选择性卤内酯化反应，它采用手性质子催化剂-N-碘代琥珀酰亚胺 (NIS) 试剂系统，其中布朗斯台德酸以低至 1 mol% 的催化剂负载量使用。在该转化中首次记录了一种调节非手性抗衡离子（与低催化剂负载下存在的中性手性配体-质子复合物等摩尔）以优化对映体选择的方法。通过这种方式，使用市售 NIS 将不饱和羧酸以高产率（高达 98% ee）转化为 γ-内酯。
• A trinuclear Zn₃(OAc)₄-3,3′-bis(aminoimino)binaphthoxide complex for highly efficient catalytic asymmetric iodolactonization
  作者：Takayoshi Arai、Noriyuki Sugiyama、Hyuma Masu、Sayaka Kado、Shinnosuke Yabe、Masahiro Yamanaka

  DOI：10.1039/c4cc02415j

  日期：——

  A 3,3'-bis(aminoimino)BINOL ligand was newly designed and synthesized for the formation of a trinuclear Zn complex upon reaction with Zn(OAc)2. Using the harmony of the tri-zinc atoms, 1 mol% Zn3(OAc)4-3,3'-bis(aminoimino)binaphthoxide catalyzed asymmetric iodolactonization in up to 99.9% ee.

  新设计并合成了3,3'-双（氨基亚氨基）BINOL配体，用于与Zn（OAc）2反应形成三核Zn络合物。使用三锌原子的和谐，1摩尔％Zn3（OAc）4-3,3'-双（氨基亚氨基）二萘嵌苯氧化物在不超过99.9％ee的条件下催化不对称碘代内酯化。
• Tertiary Aminourea-Catalyzed Enantioselective Iodolactonization
  作者：Gemma E. Veitch、Eric N. Jacobsen

  DOI：10.1002/anie.201003681

  日期：——

  Binding the anion: A highly enantioselective iodolactonization of 5‐hexenoic acids has been achieved using a tertiary aminourea‐catalyst (see scheme). The use of catalytic iodine in this process is critical to enhancing both the reactivity and enantioselectivity of the stoichiometric I+ source. The mechanism is proposed to involve binding of an iodonium imidate intermediate by the H‐bond donor catalyst

  结合阴离子：使用叔氨基脲催化剂实现了 5-己烯酸的高度对映选择性碘内酯化（参见方案）。在该过程中使用催化碘对于提高化学计量 I +源的反应性和对映选择性至关重要。该机制被认为涉及通过氢键供体催化剂结合亚胺酸碘鎓中间体。
• An asymmetric iodolactonization reaction catalyzed by a zinc bis-proline–phenol complex
  作者：Liudmila Filippova、Yngve Stenstrøm、Trond Vidar Hansen

  DOI：10.1016/j.tetlet.2013.11.028

  日期：2014.1

  The intramolecular zinc bis-proline-phenol complex 2a was found to promote enantioselective iodolactonization reactions of both electron-rich and electron-poor 5-aryl-5-hexenoic acids affording delta-iodolactones in good chemical yields with up to 82% enantiomeric excess. The reactions were found to be insensitive to air and moisture, providing an experimentally simple protocol for synthetically useful compounds. (C) 2013 Elsevier Ltd. All rights reserved.
• The Role of Ni-Carboxylate During Catalytic Asymmetric Iodolactonization Using PyBidine-Ni(OAc)2
  作者：Takayoshi Arai、Satoshi Kajikawa、Eri Matsumura

  DOI：10.1055/s-0033-1339676

  日期：——

  The combination of a PyBidine-Ni(OAc)(2) complex with a catalytic amount of iodine efficiently catalyzed asymmetric iodolactonization to generate chiral iodolactones with up to 89% enantiomeric excess. The formation of an intermediate Ni-carboxylate species from the alkenyl carboxylic acid is a key role in promoting the iodolactonization.