2,4-dimethyl-1-hydroxy-1-phenyl-3-pentanone | 61878-72-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 2,4-dimethyl-1-hydroxy-1-phenyl-3-pentanone
• 英文别名: 1-Phenyl-2-isobutyryl-propanol；1-Hydroxy-2,4-dimethyl-1-phenylpentan-3-one
• CAS: 61878-72-6
• 化学式: C₁₃H₁₈O₂
• 分子量: 206.285
• InChiKey: SCKMBACBARMBIW-UHFFFAOYSA-N

物化性质

• 沸点：
  319.0±22.0 °C(Predicted)
• 密度：
  1.026±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  15
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.46
• 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：

  2-甲基-3-戊酮 在 alkaline H₂O₂ 、 N,N-二异丙基乙胺 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 3.0h， 生成 2,4-dimethyl-1-hydroxy-1-phenyl-3-pentanone
  参考文献：
  名称：

  B,B-Dihaloalkylboranes as efficient reagents for the stereoselective synthesis of syn-aldols

  摘要：

  DOI：

  10.1016/s0040-4039(96)02448-3

文献信息

• Unusual Highly Regioselective Direct Aldol Additions with a Moisture-Resistant and Highly Efficient Titanium Catalyst
  作者：Rainer Mahrwald、Bernd Schetter

  DOI：10.1021/ol052637z

  日期：2006.1.1

  [reaction: see text] The extremely robust and water-stable tetranuclear complex Ti(4)(mu-BINOLato)(6)(mu(3)-OH)(4) was found to catalyze the direct aldol addition with high regioselectivities at the more steric alpha-encumbered side of unsymmetrical ketones. As few as 0.2 mol % loadings with this cluster were enough to afford complete conversions. The reaction proceeds very smoothly without a significant

  [反应：见正文]发现极其坚固且水稳定的四核复合物Ti（4）（mu-BINOLato）（6）（mu（3）-OH）（4）催化高羟选择性的直接羟醛加成反应。不对称酮的立体位偏侧。该簇的低至0.2 mol％的负载量足以提供完整的转化率。反应进行得非常顺利，没有大量的副产物。描述了四元立体中心的形成。
• Tetranuclear BINOL−Titanium Complex in Selective Direct Aldol Additions
  作者：Bernd Schetter、Burkhard Ziemer、Gregor Schnakenburg、Rainer Mahrwald

  DOI：10.1021/jo7014054

  日期：2008.2.1

  the direct aldol addition with high degrees of regioselectivity at the sterically more encumbered α-side of unsymmetrical ketones. The formation of quaternary stereocenters is described. Oxygen-containing ene components can also be used as starting material in these reactions. When used with aliphatic aldehydes, acetals 18 or acetals of aldol adducts 20 were observed. As few as 0.2 mol % loadings with

  极其坚固和水稳定的四核配合物的Ti 4（μ-BINOLato）6（μ 3 -OH）4（1）催化的直接醛醇加成与不对称酮的空间更作保α侧高度区域选择性。描述了四元立体中心的形成。在这些反应中，含氧的烯组分也可以用作起始原料。当与脂族醛一起使用时，观察到缩醛18或醛醇加合物20的缩醛。该催化剂1的低至0.2摩尔％的负载量足以完成反应。讨论了反应的机械方面。
• Use of boron enolates in water. The first boron enolate-mediated diastereoselective aldol reactions using catalytic boron sources
  作者：Yuichiro Mori、Juta Kobayashi、Kei Manabe、Shū Kobayashi

  DOI：10.1016/s0040-4020(02)00976-6

  日期：2002.10

  aldol reactions in water using a catalytic amount of diarylborinic acid have been developed. The reactions proceeded smoothly in the presence of a small amount of an anionic surfactant and a Brønsted acid. Water was the most suitable solvent, and organic solvents such as ether and dichloromethane were ineffective in this system. Use of bis(4-trifluoromethylphenyl)borinic acid gave high catalytic activity

  已经开发了使用催化量的二芳基硼酸在水中的高度非对映选择性的醛醇缩合反应。在少量阴离子表面活性剂和布朗斯台德酸的存在下，反应平稳进行。水是最合适的溶剂，而有机溶剂（例如乙醚和二氯甲烷）在该系统中无效。使用双（4-三氟甲基苯基）硼酸具有高催化活性。最合理的结论是，反应的活性种类是烯醇硼，这是在烯醇硼介导的非对映选择性醛醇缩合反应中催化使用硼源的第一个例子。
• Catalytic asymmetric Mukaiyama aldol reactions in aqueous media
  作者：Shū Kobayashi、Satoshi Nagayama、Tsuyoshi Busujima

  DOI：10.1016/s0040-4020(99)00440-8

  日期：1999.7

  Chiral copper(II)-catalyzed asymmetric aldol reactions of silyl enol ethers with aldehydes (the Mukaiyama aldol reaction) have been performed in an ethanol-water solution. The use of the protic solvent including water is a key to achieve these reactions. Moreover, a catalytic asymmetric aldol reaction in pure water without using organic solvents has also been successfully carried out. This report has

  已经在乙醇-水溶液中进行了手性铜（II）催化的甲硅烷基烯醇醚与醛的不对称醛醇缩合反应（Mukaiyama醛醇缩合反应）。使用质子溶剂包括水是实现这些反应的关键。此外，还已经成功地在不使用有机溶剂的情况下在纯水中进行了催化不对称醛醇缩合反应。该报告提出并证明了催化不对称醛醇缩合反应中溶剂的新概念。
• Mixed Alkylamido Aluminate as a Kinetically Controlled Base
  作者：Hiroshi Naka、James V. Morey、Joanna Haywood、Dana J. Eisler、Mary McPartlin、Felipe García、Hironaga Kudo、Yoshinori Kondo、Masanobu Uchiyama、Andrew E. H. Wheatley

  DOI：10.1021/ja804749y

  日期：2008.12.3

  The mechanisms by which directed ortho metalation (DoM) and postmetalation processes occur when aromatic compounds are treated with mixed alkylamido aluminate i-BU3Al(TMP)Li (TMP-aluminate 1; TMP = 2,2,6,6-tetramethylpiperidide) have been investigated by computation and X-ray diffraction. Sequential reaction of ArC(=O)N(i-Pr)(2) (Ar = phenyl, 1-naphthyl) with t-BuLi and t-Bu3Al in tetrahydrofuran affords [2-(i-Bu3Al)CmHnC(=O)N(i-Pr)(2)]Li center dot 3THF (m = 6, n = 4, 7; m = 10, n = 6, 8). These data advance the structural evidence for ortho-aluminated functionalized aromatics and represent model intermediates in DoM chemistry. Both 7 and 8 are found to resist reaction with HTMP, suggesting that ortho-aluminated aromatics are incapable of exhibiting stepwise deprotonative reactivity of the type recently shown to pertain to the related field of ortho zincation chemistry. Density functional theory calculations corroborate this view and reveal the existence of substantial kinetic barriers both to one-step alkyl exchange and to amido-alkyl exchange after an initial amido deprotonation reaction by aluminate bases. Rationalization of this dichotomy comes from an evaluation of the inherent Lewis acidities of the Al and Zn centers. As a representative synthetic application of this high kinetic reactivity of the TMP-aluminate, the highly regioselective deprotonative functionalization of unsymmetrical ketones both under mild conditions and at elevated temperatures is also presented.