(2R*,3S*)-4-phenyl-4-hydroxy-3-methyl-2-butanone | 81640-13-3

• 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: (2R*,3S*)-4-phenyl-4-hydroxy-3-methyl-2-butanone
• 英文别名: (anti)-4-hydroxy-3-methyl-4-phenylbutan-2-one；anti-1-Hydroxy-2-methyl-1-phenylbutan-3-one；anti-4-hydroxy-3-methyl-4-phenylbutan-2-one；4-hydroxy-3-methyl-4-phenyl-butan-2-one；4-hydroxy-3-methyl-4-phenyl-2-butanone；4-hydroxy-3-methyl-4-phenylbutan-2-one；(3S,4R)-4-hydroxy-3-methyl-4-phenylbutan-2-one
• CAS: 81640-13-3
• 化学式: C₁₁H₁₄O₂
• 分子量: 178.231
• InChiKey: PSMPCPHOQAAKLW-LDYMZIIASA-N

物化性质

• 沸点：
  294.3±20.0 °C(Predicted)
• 密度：
  1.063±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 重原子数：
  13
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.36
• 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：

  苯甲醛 在 二甲基硫 、 臭氧 作用下， 反应 20.17h， 生成 (2R*,3S*)-4-phenyl-4-hydroxy-3-methyl-2-butanone
  参考文献：
  名称：

  关于α-甲基丁-2-烯基锡烷与醛之间反应的立体选择性

  摘要：

  α-甲基丁-2-烯基锡烷（7）-（9）在加热下与醛发生立体反应，形成抗-5-羟基-4-甲基-Z-戊-2-烯（16）和（17）。在BF 3 ·Et 2 O的存在下，主要产物是相应的syn-5-羟基-4-甲基-E-戊-2-烯（22）和（23）。

  DOI：

  10.1016/0040-4020(89)80012-2

文献信息

• Catalytic asymmetric synthesis of β-hydroxy ketones by palladium-catalyzed asymmetric 1,4-disilylation of α,β-unsaturated ketones
  作者：Yonetatsu Matsumoto、Tamio Hayashi、Yoshihiko Ito

  DOI：10.1016/s0040-4020(01)80758-4

  日期：1994.1

  1,4-Disilylation of β,β-unsaturated ketones with 1,1-dichloro-l-phenyl-2,2,2-trimethyldisilane proceeded in the presence of phosphine-palladium catalysts in benzene. High enantio-selectivity (up to 92%) was observed in the disilylation with dichloro[(R)-2,2′-bis(diphenylphosphino)-1,1′-binaphthyl]palladium(II) as a catalyst (0.5 mol %). The disilylation products, 1-(trimethyisilyloxy)-3-(dichlorophenylsilyl)propenes

  在苯存在膦-钯催化剂的情况下，将β，β-不饱和酮与1,1-二氯-1-苯基-2,2,2-三甲基乙硅烷进行1,4-二甲化。使用二氯[（R）-2,2'-双（二苯基膦基）-1,1'-联萘]钯（II）（0.5 mol％ ）。容易将二甲硅烷基化产物1-（三甲基甲硅烷基氧基）-3-（二氯苯基甲硅烷基）丙烯转化为旋光性的α-未取代或抗α-取代的β-（苯基二甲基甲硅烷基）酮，其氧化反应生成相应的旋光性β-羟基酮高产。
• Tetrahedral boronates as basic catalysts in the aldol reaction
  作者：Tobias Müller、Kristina Djanashvili、Joop A. Peters、Isabel W.C.E. Arends、Ulf Hanefeld

  DOI：10.1515/znb-2015-0029

  日期：2015.8.1

  β-Hydroxyketones are versatile building blocks in organic synthesis, which can be conveniently synthesized from ketones and aldehydes by aldol reactions. Unfortunately, these reactions often suffer from dehydration of the initially formed β-hydroxyketones. Previously, tetrahedral 3,5-difluorophenylborate was shown to be an efficient and selective catalyst for this reaction. The present investigation concerns the catalytic performance of phenyl borates with different substitution patterns in the aldol reaction. It appears that the dehydration reaction can be suppressed by selecting substituents and substituent positions with reduced electron withdrawing effects on the borate function. Optimal suppression of the dehydration of β-hydroxyketones was obtained for compounds corresponding to phenylboronic acids with a pK _a > 7. The reactions between benzaldehyde and butanone or 3-pentanone did not show diastereoselectivity, which suggests that the catalysts merely act as bases rather than as templates for the transition state of the aldol reaction. Sterically more demanding ketones were not converted.

  β-羟基酮是有机合成中多用途的构建模块，可以通过醛和酮的羟醛反应方便地合成。不幸的是，这些反应常常受到最初形成的β-羟基酮脱水的困扰。之前的研究表明，四面体3,5-二氟苯基硼酸酯是这种反应的高效且选择性催化剂。当前的调查研究涉及到不同取代模式的苯基硼酸酯在羟醛反应中的催化性能。看来，通过选择具有减少硼酸功能电子吸引效果的取代基和取代基位置，可以抑制脱水反应。β-羟基酮的脱水反应在对应于苯硼酸的化合物的pK_a > 7时得到了最佳抑制。苯甲醛与丁酮或3-戊酮的反应没有显示出对映选择性，这表明催化剂仅仅是作为碱而非羟醛反应过渡态的模板。空间位阻更大的酮没有发生转化。

• 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。
• A New Halogen-Exchange Reaction between Sn–F and Li–X: Selective 1,2- and 1,4-Reductions of<i>α,β</i>-Unsaturated Ketones and Effects of Halogen Substituents on the Regioselectivity of Organotin Hydrides
  作者：Takayo Moriuchi-Kawakami、Haruo Matsuda、Ikuya Shibata、Masato Miyatake、Toshihiro Suwa、Akio Baba

  DOI：10.1246/bcsj.72.465

  日期：1999.3

  We have found that halogen-exchange occurs effectively between Sn–F and Li–X (X = I, Br, Cl) in tin hydride reagents. This fact induced a complete change in the regiochemistry in the reductions of α,β-unsaturated ketones 1 with Bu2SnH2–Bu2SnF2 (Reagent A): the use of Reagent A in combination with HMPA performed 1,2-reductions, while the addition of LiI to Reagent A achieved 1,4-reductions. It was demonstrated

  我们发现，在氢化锡试剂中，Sn-F 和 Li-X（X = I，Br，Cl）之间有效地发生了卤素交换。这一事实导致 α,β-不饱和酮 1 用 Bu2SnH2–Bu2SnF2（试剂 A）还原的区域化学发生完全变化：试剂 A 与 HMPA 结合使用进行 1,2-还原，而添加 LiI试剂 A 实现了 1,4-还原。结果表明，有机锡氢化物的区域选择性很大程度上取决于与锡原子相连的卤素取代基的性质。
• Highly Diastereo- and Enantioselective Direct Aldol Reactions of Aldehydes and Ketones Catalyzed by Siloxyproline in the Presence of Water
  作者：Seiji Aratake、Takahiko Itoh、Tsubasa Okano、Norio Nagae、Tatsunobu Sumiya、Mitsuru Shoji、Yujiro Hayashi

  DOI：10.1002/chem.200700363

  日期：2007.12.17

  study, affording the aldol product with excellent diastereo- and enantioselectivities, these two catalysts generating opposite enantiomers. Water affects the selectivity, and poor results are obtained under neat reaction conditions or in dry organic solvents. More than three equivalents of water are required for the best diastereo- and enantioselectivities, while three equivalents is the recommended amount

  已经开发了基于脯氨酸的有机催化剂，用于在水存在下醛和酮的高度对映选择性，直接的醛醇缩合反应。尽管已证明几种表面活性剂-脯氨酸组合的催化剂有效，但具有疏水部分的脯氨酸衍生物，例如反式-甲硅烷氧基-L-脯氨酸和顺-甲硅烷氧基-D-脯氨酸，可以容易地从相同的市售4-羟基-已经发现，L-脯氨酸是这项研究中最有效的有机催化剂，为醛醇产物提供了极佳的非对映体和对映体选择性，这两种催化剂产生相反的对映体。水会影响选择性，在纯净的反应条件下或在干燥的有机溶剂中，收效差。为了获得最佳的非对映选择性和对映选择性，需要超过三当量的水，从综合的角度来看，建议的当量为三当量。反应在有机相中进行，并且也在大量水的存在下进行。描述了在包括纯化步骤在内的最少使用有机溶剂的情况下大规模制备羟醛的方法。