3-hydroxy-2-methyl-1-phenyl-3-(4'-chlorophenyl)-1-propanone

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 直链 1,3-二芳基丙烷
• 英文名称: 3-hydroxy-2-methyl-1-phenyl-3-(4'-chlorophenyl)-1-propanone
• 英文别名: 3-(4-chlorophenyl)-3-hydroxy-2-methyl-1-phenylpropan-1-one；3-(4-chlorophenyl)-3-hydroxy-2-methyl-1-phenyl-1-propanone；(2S,3S)-3-(4-chlorophenyl)-3-hydroxy-2-methyl-1-phenylpropan-1-one
• 化学式: C₁₆H₁₅ClO₂
• 分子量: 274.747
• InChiKey: YKJJINLOTHGNPP-BZNIZROVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  19
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.19
• 拓扑面积：
  37.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  4-氯苯甲醛 、 1-phenyl-1-trimethylsiloxypropene 在 (2R,2'R)-dimethyl 2,2'-(1,7-dioxa-4,10-diazacyclododecane-4,10-diyl)dipropanoate 、 europium(III) trifluoromethanesulfonate 作用下， 以 乙醇 、 水 为溶剂， 反应 168.0h， 以75%的产率得到3-hydroxy-2-methyl-1-phenyl-3-(4'-chlorophenyl)-1-propanone
  参考文献：
  名称：

  A New Class of Ligands for Aqueous, Lanthanide-Catalyzed, Enantioselective Mukaiyama Aldol Reactions

  摘要：

  The development of aqueous methods for generating enantiopure beta-hydroxy carbonyl compounds is an important goal because these subunits compose many bioactive compounds and the ability to synthesize these groups in water has environmental and cost benefits. In this communication, we report a new class of ligands for aqueous, lanthanide-catalyzed, asymmetric Mukaiyama aldol reactions for the synthesis of chiral beta-hydroxy ketones. Furthermore, we have used luminescence-decay measurements to unveil mechanistic information regarding the catalytic reaction via changes in water-coordination number. The precatalysts presented here yielded beta-hydroxy carbonyls from aliphatic and aryl substrates with outstanding syn:anti ratios and enantiometric excesses of up to 49:1 and 97%, respectively.

  DOI：

  10.1021/ja107197p

文献信息

• Synthetic control leading to chiral compounds
  作者：Teruaki Mukaiyama、Nobuharu Iwasawa、Rodney W. Stevens、Toru Haga

  DOI：10.1016/s0040-4020(01)82423-6

  日期：1984.1

  A highly diastereoselective cross aldol reaction is developed using divalent tin enolates formed from stannous trifluoromethanesulfonate and carbonyl compounds. The reaction is extended to a highly enantioselective cross aldol reaction employing chiral diamines derived from (S)-proline as ligands.

  使用由三氟甲烷磺酸亚锡和羰基化合物形成的二价烯醇锡开发了高度非对映选择性的交叉醇醛缩合反应。使用衍生自（S）-脯氨酸的手性二胺作为配体，将反应扩展至高度对映选择性的交叉羟醛反应。
• Aqueous Asymmetric Mukaiyama Aldol Reaction Catalyzed by Chiral Gallium Lewis Acid with Trost-Type Semi-Crown Ligands
  作者：Hui-Jing Li、Hong-Yu Tian、Yan-Chao Wu、Yong-Jun Chen、Li Liu、Dong Wang、Chao-Jun Li

  DOI：10.1002/adsc.200505089

  日期：2005.7

  generates highly effective chiral gallium Lewis acid catalysts for aqueous asymmetric aldol reactions of aromatic silyl enol ethers with aldehydes. A ligand-acceleration effect was observed. Water is essential for obtaining high diastereoselectivity and enantioselectivity. The p-phenyl substituent in aromatic silyl enol ether (2 h) plays an important role and increases the enantioselectivity up to 95%

  Ga（OTf）3与手性半冠配体（1a – e）的结合产生了高效的手性镓路易斯酸催化剂，用于芳族甲硅烷基烯醇醚与醛的水性不对称羟醛反应。观察到配体促进作用。水对于获得高非对映选择性和对映选择性是必不可少的。芳基甲硅烷基烯醇醚中的对苯基取代基（2 h）起着重要作用，对映选择性提高至95％ee。尽管脂族甲硅烷基烯醇醚的对映选择性低，而甲硅烷基烯酮缩醛容易在含水醇中水解，但甲硅烷基烯酮硫缩醛的醛醇缩合反应（12）在镓-路易斯酸催化剂的存在下与醛一起以合理的收率和高的非对映异构体（高达99：1）和对映选择性（高达96％ee）提供β-羟基硫酯。
• Gallium(III) Triflate Catalyzed Diastereoselective Mukaiyama Aldol Reaction by Using Low Catalyst Loadings
  作者：Baptiste Plancq、Lyse Carole Justafort、Mathieu Lafantaisie、Thierry Ollevier

  DOI：10.1002/ejoc.201301100

  日期：2013.10

  A mild method for the diastereoselective Mukaiyama aldol reaction is reported. By using a low loading of the gallium(III) triflate catalyst (down to 0.01 mol-%), the transformation proceeds efficiently to afford the corresponding β-hydroxy ketones in yields up to 92 %. To the best of our knowledge, this is the first report of a metal triflate acting as a safe, bench-stable, and slow-releasing source

  报道了非对映选择性 Mukaiyama 醛醇反应的温和方法。通过使用低负载量的三氟甲磺酸镓 (III) 催化剂（低至 0.01 mol-%），转化有效地进行，以高达 92% 的产率提供相应的 β-羟基酮。据我们所知，这是首次报道金属三氟甲磺酸盐可作为安全、长期稳定且缓慢释放的三氟甲磺酸来源，用于向山羟醛反应。
• Synthesis of β‐Hydroxy and β‐Amino Ketones from Allylic Alcohols Catalyzed by Ru(η ⁵ ‐C ₅ Ph ₅ )(CO) ₂ Cl
  作者：Agnieszka Bartoszewicz、Martina M. Jeżowska、Kévin Laymand、Juri Möbus、Belén Martín‐Matute

  DOI：10.1002/ejic.201101014

  日期：2012.3

  An efficient method for the synthesis of beta-hydroxy and beta-amino ketones from allylic alcohols catalyzed by Ru(5-C5Ph5)(CO)2Cl is described. The influence of the stereoelectronic properties of ...

  描述了一种由 Ru(5-C5Ph5)(CO)2Cl 催化的烯丙醇合成 β-羟基和 β-氨基酮的有效方法。立体电子特性的影响...
• Highly Diastereoselective Aldol Synthesis from<i>α</i>-Iodo Ketones in Aqueous Media
  作者：Ikuya Shibata、Masatsugu Kawasaki、Makoto Yasuda、Akio Baba

  DOI：10.1246/cl.1999.689

  日期：1999.7

  Highly diastereoselective aldol synthesis from α-iodo ketones was promoted under aqueous conditions by a distannane system, (n-Bu3Sn)2, n-Bu2SnF2 and HMPA. Aqueous solutions of acetaldehyde, formaldehyde and pivaraldehyde were applicable to give β-hydroxy ketones effectively.

  在水性条件下，二锡烷系统、(n-Bu3Sn)2、n-Bu2SnF2 和 HMPA 促进了由 α-碘酮合成的高度非对映选择性羟醛。乙醛、甲醛和新戊醛的水溶液适用于有效地得到β-羟基酮。