meso-2,4-diiodo-3-pentanone | 400643-56-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: meso-2,4-diiodo-3-pentanone
• 英文别名: 2,4-diiodo-3-pentanone；3-Pentanone, 2,4-diiodo-；2,4-diiodopentan-3-one
• CAS: 400643-56-3
• 化学式: C₅H₈I₂O
• 分子量: 337.927
• InChiKey: YXWFMIGIPJOXGJ-UHFFFAOYSA-N

物化性质

• 沸点：
  260.9±25.0 °C(Predicted)
• 密度：
  2.305±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  8
• 可旋转键数：
  2
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  meso-2,4-diiodo-3-pentanone 在 三乙胺 、 potassium iodide 作用下， 以 丙酮 为溶剂， 反应 5.0h， 以47%的产率得到α-hydroxyethylketone
  参考文献：
  名称：

  A novel synthesis of α-hydroxy- and α,α′-dihydroxyketone from α-iodo and α,α′-diiodo ketone using photoirradiation

  摘要：

  A novel reaction of alpha-iodo ketone (alpha-iodocycloalkanone, alpha-iodo-beta-alkoxy ester, and alpha-iodoacyclicketone) with irradiation under a high-pressure mercury lamp gave the corresponding alpha-hydroxyketone in good yields. In the case of alpha,alpha'-diiodo ketone, alpha,alpha'-dihydroxyketone which little has been reported until now was obtained. This reaction affords a new, clean and convenient synthetic method for alpha-hydroxy- and alpha,alpha'-dihydroxyketone. (C) 2003 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2003.10.082
• 作为产物：
  描述：

  3-戊酮 在 ammonium cerium(IV) nitrate 、 碘 作用下， 以 水 、 溶剂黄146 为溶剂， 反应 30.0h， 以62%的产率得到meso-2,4-diiodo-3-pentanone
  参考文献：
  名称：

  A Newα,α′-Diiodination of Ketones Using Iodine-Cerium(IV) Ammonium Nitrate

  摘要：

  使用碘-铈(IV)硝酸铵在乙酸或丙酮中直接碘化一些酮，可以高收率地得到相应的α,α′-二碘酮。对于环十二烷酮(4)、3-戊酮(5)和5-壬酮(6)，优先得到顺式(内消旋)化合物[2,12-二碘环十二烷酮(12)、2,4-二碘-3-戊酮(13)和4,6-二碘-5-壬酮(14)]。

  DOI：

  10.1246/bcsj.67.271

文献信息

• New methodology for the [4+3] cycloaddition reactions: generation of oxyallyl cations from α,α′-diiodoketones under sonochemical or thermal conditions
  作者：Angel M Montaña、Pedro M Grima

  DOI：10.1016/s0040-4039(01)01671-9

  日期：2001.10

  A new methodology to perform [4+3] cycloaddition reactions of suitable dienes and 1,3-dimethyl-2-oxyallyl cations is presented. The reaction is carried out starting from commercially available dienes and easy-handling α,α′-diiodoketones, which are reduced by the Zn/Cu couple to generate the oxyallyl cation as intermediate. The reaction is carried out under mild thermal or sonochemical conditions at

  提出了一种进行合适的二烯与1,3-二甲基-2-氧基烯丙基阳离子的[4 + 3]环加成反应的新方法。该反应从可商购获得的二烯和易于处理的α，α′-二碘酮开始进行，所述α，α′-二碘酮通过Zn / Cu对被还原以产生作为中间体的羟基烯丙基阳离子。该反应在温和的热或声化学条件下于低温（0至-44°C）下进行，反应时间短（<15分钟）。该方法学代表了基于其他还原剂或从更复杂的羟烯丙基阳离子前体开始的实际程序的良好替代性方面。
• Use of the<i>p</i>-Tolylsulfinyl Group as a Chiral Inductor in Stereoselective [4+3] Cycloaddition Reactions: Preparation of Enantiopure Polysubstituted 8-Oxabicyclo[3.2.1]oct-6-en-3-one Systems Having up to Five Stereocenters
  作者：Ángel M. Montaña、Pedro M. Grima、Consuelo Batalla、Francisca Sanz、Gabriele Kociok-Köhn

  DOI：10.1002/ejoc.201301814

  日期：2014.5

  The use of the p-tolylsulfinyl group as a chiral inductor in stereoselective [4+3] cycloaddition reactions has made possible the preparation of enantiopure polysubstituted 8-oxabicyclo[3.2.1]oct-6-en-3-one systems having up to five stereocenters. The presence in the furan diene of a susbtituent at the 3-position bearing an atom with lone-pair electrons propitiates the coordination of a metallic atom

  在立体选择性 [4+3] 环加成反应中使用对甲苯基亚磺酰基作为手性诱导剂使得制备对映纯的多取代 8-氧杂双环 [3.2.1]oct-6-en-3-one 系统成为可能五个立体中心。呋喃二烯中 3 位带有孤对电子原子的取代基的存在促进了亚砜和 R3“配体”基团对金属原子的配位。这种螯合效应，连同 R3 和亚砜基团的立体电子需求，显着降低了环状过渡态中二烯部分的构象自由度，从而导致观察到的立体选择性。通过在呋喃环中选择合适的取代基，可以获得 100:0 的顺-反和 100:0 的内-外非对映选择性。可以达到高达 100% 的 π 面非对映选择性（去除亚砜基团后的对映选择性）。取决于呋喃底物，产率在 50-80% 的范围内。然而，如果呋喃二烯配有失活的吸电子取代基，在某些反应条件下观察到低转化率，但总是具有优异的化学和立体选择性。在呋喃环的 C-3 处引入给电子取代基后，转化率和产率增加。但始终
• Photo-irradiation of α-halo carbonyl compounds: a novel synthesis of α-hydroxy- and α,α′-dihydroxyketones
  作者：Wen Chai、Akihiro Takeda、Makoto Hara、Shun-Jun Ji、C. Akira Horiuchi

  DOI：10.1016/j.tet.2005.01.010

  日期：2005.2

  The reaction of g.-halo ketones (alpha-iodocycloalkanones, alpha-bromocycloalkanones, alpha-iodo-beta-alkoxy esters, and alpha-iodoacyclic-ketones) with irradiation under a high-pressure mercury lamp gave the corresponding alpha-hydroxyketones in good yields. For alpha-bromoketones, it was found that alpha-hydroxylation does not occur. However, alpha-bromoketones were convened into a-hydroxyketones in the presence of KI. In the case of alpha,alpha(1)-diiodo ketones, alpha,alpha(1)-dihydroxyketones, which up to now have scarcely been reported, were obtained. This reaction affords a new, clean and convenient synthetic method for alpha-hydroxy- and alpha,alpha(1)-dihydroxyketones. (C) 2005 Elsevier Ltd. All rights reserved.
• Asymmetry induction on the [4C(4π)+3C(2π)] cycloaddition reaction of C2-functionalized furans: influence of the chiral auxiliary nature
  作者：Angel M Montaña、Pedro M Grima

  DOI：10.1016/s0040-4020(02)00452-0

  日期：2002.6

  The study of the pi-facial diastereoselectivity in the [4+3] cycloaddition reaction of thirteen different chiral 2-substituted furans with oxyallyl cations, under sonochemical and/or thermal conditions, is presented. In almost all studied furans, a cis diastereoselectivity and a high endo diastereoselectivity is observed. Decreasing the distance between the closest stereocenter of the chiral auxiliary and the reactive C2-carbon of the furan ring, increases the pi-facial diastereoselectivity, especially by using chiral furyl-sulfoxides. (C) 2002 Elsevier Science Ltd. All rights reserved.
• [4+3] Cycloaddition of C-3 substituted furans. Stereoselectivity induced by coordination effects
  作者：Ángel M. Montaña、Pedro M. Grima、María Castellví、Consuelo Batalla、Mercè Font-Bardia

  DOI：10.1016/j.tet.2012.09.070

  日期：2012.12

  Several C-3 substituted furans with chelating groups have been reacted with 2,3-dibromo-3-pentanone in the presence of a reducing metal, resulting in the formation of [4+3]-cycloadducts with complete cis-trans and endo-exo diastereoselectivity and in excellent yield. A certain variability of the conversion and reaction yield could be observed, when changing the reaction conditions, but in all cases the stereoselectivity was complete, compared to that of C-3 substituted furans with non-chelating groups. Also, a general method of assignment of stereochemistry of cycloadducts has been established by NMR, considering diagnostic patterns of signals with different multiplicity and chemical shifts depending on the stereochemistry of diastereomeric cycloadducts. (C) 2012 Elsevier Ltd. All rights reserved.