2,4-dimethyl-3-hydroxy-1-phenyl-1-pentanone | 73739-28-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2,4-dimethyl-3-hydroxy-1-phenyl-1-pentanone
• 英文别名: 2,4-dimethyl-3-hydroxy-1-phenylpentan-1-one；3-hydroxy-2,4-dimethyl-1-phenyl-1-pentanone；threo-2,4-dimethyl-3-hydroxy-1-phenyl-1-pentanone；(2R,3R)-1-Phenyl-2,4-dimethyl-3-hydroxy-1-pentanone；(2R,3R)-3-hydroxy-2,4-dimethyl-1-phenylpentan-1-one
• CAS: 73739-28-3；73739-37-4；93250-18-1
• 化学式: C₁₃H₁₈O₂
• 分子量: 206.285
• InChiKey: FTPHOAUCRXCRBV-ZYHUDNBSSA-N

物化性质

• 沸点：
  325.4±25.0 °C(Predicted)
• 密度：
  1.020±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 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

安全信息

• 海关编码：
  2914400090

反应信息

• 作为反应物：
  描述：

  2,4-dimethyl-3-hydroxy-1-phenyl-1-pentanone 在 lithium hydride 、 四氯化钛 、 硼烷四氢呋喃络合物 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 0.67h， 生成 (4R,5R,6S)-4-Isopropyl-5-methyl-6-phenyl-[1,3,2]dioxaborinane
  参考文献：
  名称：

  The Role of theα-Stereogenic Center in the Control of Stereoselection in the Reduction ofα-Alkyl-β-hydroxy Ketones: A Highly Diastereoselective Protocol for the Synthesis of 1,2-syn-2-Alkyl-1,3-diols

  摘要：

  Accurate investigations on the role played by an alpha-stereogenic center in controlling the reduction of various classes of beta-hydroxy ketones allowed us to set up a general and highly diastereoselective protocol for the synthesis of 2-alkyl-1,3-diols with 1,2-syn relationship. This methodology is based on the conversion of a beta-hydroxy ketone into the corresponding titanium alcoholate that permits us to organize the substrate in a stable and rigid structure, which stereofacially favors attacking hydride ions. The use of THF as solvent makes available a variety of hydride donors that cover a large spectrum of steric demand: the choice of the more appropriate one depends on the conformational stability of the cyclic intermediate. Excellent results are obtained also in the presence of an additional stereogenic center in the beta-position, even if it exerts a concordant or an opposite steric effect with respect to the alpha-substituent.

  DOI：

  10.1002/1521-3765(20000717)6:14<2590::aid-chem2590>3.0.co;2-x
• 作为产物：
  描述：

  2-iodo-1-phenylpropan-1-one 在 2,6-二甲基吡啶 作用下， 以 四氢呋喃 为溶剂， 反应 13.0h， 生成 2,4-dimethyl-3-hydroxy-1-phenyl-1-pentanone
  参考文献：
  名称：

  通过由 α-碘酮和 9-BBN-H 生成的硼烯醇化物进行立体选择性交叉羟醛反应

  摘要：

  通过用 9-BBN-H 处理 α-碘酮，原位顺利生成硼烯醇化物，并通过与各种醛在低温下连续反应以高度非对映选择性的方式生成醛醇。

  DOI：

  10.1246/cl.2002.698

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。
• Direct, practical, and powerful crossed aldol additions between ketones and ketones or aldehydes utilizing environmentally benign TiCl4–Bu3N reagent
  作者：Yoo Tanabe、Noriaki Matsumoto、Takahiro Higashi、Tomonori Misaki、Tomotaka Itoh、Misako Yamamoto、Kumi Mitarai、Yoshinori Nishii

  DOI：10.1016/s0040-4020(02)00977-8

  日期：2002.10

  benign method is advantageous from a green chemical viewpoint with regard to yield, substrates variation, reagent availability, and simple procedures. This method was applied to a short step formal synthesis of (R)-muscone, a natural macrocyclic musk.

  在酮和酮或醛之间进行了有效的TiCl 4 -Bu 3 N-（cat。TMSCl）促进的羟醛添加。从绿色化学观点来看，该环境友好方法在产率，底物变化，试剂可用性和简单程序方面是有利的。该方法用于天然大环麝香（R）-muscone的短步正式合成。
• Boron-Mediated Aldol Reaction of Carboxylic Esters:  Complementary Anti- and Syn-Selective Asymmetric Aldol Reactions
  作者：Tadashi Inoue、Ji-Feng Liu、Dana C. Buske、Atsushi Abiko

  DOI：10.1021/jo0257896

  日期：2002.7.1

  The boron-mediated aldol reaction of carboxylic esters is described in detail. Contrary to the general belief that carboxylic esters are inert under the condition of the boron enolate formation, propionate esters are enolized with certain combinations of a boron triflate and an amine. More importantly, the stereochemical course of the aldol reaction can be controlled by the judicious selection of the

  详细描述了硼介导的羧酸酯的羟醛反应。与通常认为羧酸酯在烯醇硼形成的条件下是惰性的一般看法相反，丙酸酯被三氟甲磺酸硼和胺的某些组合烯醇化。更重要的是，可以通过明智地选择烯醇化试剂来控制羟醛反应的立体化学过程。用c-Hex2BOTf和三乙胺处理丙酸酯可制得抗醛醇缩合产物，而用Bu2BOTf和二异丙基乙胺处理丙酸酯可在与醛反应后选择性地生成顺醛醇缩合产物。已经开发了具有结构相关的，容易获得的手性去甲麻黄碱衍生的丙酸酯的互补抗和顺选择性不对称醛醇缩合反应。
• STANNOUS TRIFLATE: A NEW ALDOL REACTION VIA DIVALENT TIN ENOLATES
  作者：Teruaki Mukaiyama、Rodney. W. Stevens、Nobuharu Iwasawa

  DOI：10.1246/cl.1982.353

  日期：1982.3.5

  Divalent tin enolates formed from stannous triflate and ketones react with carbonyl compounds under mild conditions to give the corresponding aldol products in good yields. In the case of cross-cou...

  由三氟甲磺酸亚锡和酮形成的二价锡烯醇化物在温和条件下与羰基化合物反应，以良好的产率得到相应的醛醇产物。在交叉的情况下...
• From Allylic Alcohols to Aldols through a New Nickel-Mediated Tandem Reaction: Synthetic and Mechanistic Studies
  作者：David Cuperly、Julien Petrignet、Christophe Crévisy、René Grée

  DOI：10.1002/chem.200501555

  日期：2006.4.12

  racemic compounds. However, it was possible to use asymmetric synthesis for the preparation of optically active aldols. Various mechanistic studies have been performed using, for instance, a deuterated alcohol or a deuterated catalyst. They gave strong support to a mechanism involving first a transition-metal-mediated isomerization of the allylic alcohol into the free enol, followed by the addition of

  氢化镍型配合物已成功开发为烯丙基醇与醛的串联异构化-醛醇缩合反应的催化剂。反应条件的优化表明，助催化剂，例如MgBr2，对反应动力学和醛醇的收率具有非常积极的影响。在这样的优化条件下[NiHCl（dppe）] + MgBr（2）3-5摩尔％）}，该反应以良好的收率获得了醇醛。这是在温和条件下发生的全原子经济型反应。此外，它具有广泛的烯丙基醇范围，并且与多种醛相容，包括非常庞大的衍生物。该反应是完全区域选择性的，但是它表现出低的立体选择性，除了在甲醇中心具有大取代基的烯丙基醇。手性非外消旋催化剂的使用并不成功，仅得到外消旋化合物。然而，可以使用不对称合成来制备旋光醇醛。已经使用例如氘代醇或氘代催化剂进行了各种机理研究。他们提供了一种机制的强有力的支持，该机制包括首先将过渡金属介导的烯丙基醇异构化成游离烯醇，然后在“羟基-羰基-烯”型反应中将后者的中间体加到醛上。这些结果证实，烯丙醇可以被认