(2R*,3R*)-4-phenyl-4-hydroxy-3-methyl-2-butanone | 75600-09-8

• 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*,3R*)-4-phenyl-4-hydroxy-3-methyl-2-butanone
• 英文别名: (syn)-4-hydroxy-3-methyl-4-phenylbutan-2-one；syn-1-Hydroxy-2-methyl-1-phenylbutan-3-one；syn-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；2-Butanone, 4-hydroxy-3-methyl-4-phenyl-, (3R,4R)-；(3R,4R)-4-hydroxy-3-methyl-4-phenylbutan-2-one
• CAS: 75600-09-8
• 化学式: C₁₁H₁₄O₂
• 分子量: 178.231
• InChiKey: PSMPCPHOQAAKLW-GZMMTYOYSA-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

• 作为反应物：
  描述：

  (2R*,3R*)-4-phenyl-4-hydroxy-3-methyl-2-butanone 在 吡啶 、 4-二甲氨基吡啶 、 ruthenium trichloride 、 zinc borohydride 、 1-羟基苯并三唑 、 高碘酸 、 N,N'-二环己基碳二亚胺 作用下， 以 四氯化碳 、 乙醚 、 二氯甲烷 、 水 、 乙腈 为溶剂， 反应 20.5h， 生成
  参考文献：
  名称：

  Stereoselective Synthesis of an Immunomodulator (+)-Conagenin Using ­Dirhodium(II)-Catalyzed C-H Amination and Chelation-Controlled ­Reductions as Key Steps

  摘要：

  使用商业可得的光学活性甲基-3-羟基-2-甲基丙酸酯，通过二铑(II)催化的C-H胺化和螯合控制还原作为关键步骤，实现了免疫调节剂(+)-conagenin的立体选择性合成。

  DOI：

  10.1055/s-2006-933145
• 作为产物：
  描述：

  erythro-2-<(trimethylsilyl)oxy>-5-hydroxy-2,4-dimethyl-5-phenylpentan-3-one 在 对甲苯磺酸 、 高碘酸 作用下， 以 二氯甲烷 为溶剂， 反应 21.0h， 生成 (2R*,3R*)-4-phenyl-4-hydroxy-3-methyl-2-butanone
  参考文献：
  名称：

  Acyclic stereoselection. 10. A general synthesis of erythro-.alpha.-alkyl-.beta.-hydroxy ketones

  摘要：

  DOI：

  10.1021/jo00314a047

文献信息

• 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。

• Cu‐Catalyzed Chemoselective Preparation of 2‐(Pinacolato)boron‐Substituted Allylcopper Complexes and their In Situ Site‐, Diastereo‐, and Enantioselective Additions to Aldehydes and Ketones
  作者：Fanke Meng、Hwanjong Jang、Byunghyuck Jung、Amir H. Hoveyda

  DOI：10.1002/anie.201301018

  日期：2013.5.3

  Sustainable, efficient, selective: A three‐component, single‐vessel Cu‐catalyzed method for chemo‐, diastereo‐, and enantioselective conversion of B2(pin)2, monosubstituted allenes, and aldehydes or ketones to 2‐B(pin)‐substituted homoallylic alkoxides is described. Subsequent functionalization delivers valuable products in up to >98:2 d.r. and 97:3 e.r. (see scheme).

  可持续、高效、选择性：一种三组分、单容器铜催化方法，用于 B 2 (pin) 2、单取代丙二烯和醛或酮向 2-B(pin) 的化学、非对映和对映选择性转化描述了-取代的高烯丙基醇盐。随后的功能化可提供高达 >98:2 dr 和 97:3 er 的有价值的产品（参见方案）。
• 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。
• Rhodium-Catalyzed Cross-Aldol Reaction: In Situ Aldehyde-Enolate Formation from Allyloxyboranes and Primary Allylic Alcohols
  作者：Luqing Lin、Kumiko Yamamoto、Shigeki Matsunaga、Motomu Kanai

  DOI：10.1002/anie.201205680

  日期：2012.10.8

  Dip in! A Rh/dippf catalyst generates aldehyde‐derived enol boranes at ambient temperature by isomerization of allyloxy‐ and homoallyloxyboranes. A one‐pot isomerization/cross‐aldol sequence provides aldehyde–aldehyde adducts in good yield with syn selectivity. Direct use of primary allylic and homoallylic alcohols was also achieved.

  蘸！Rh / dippf催化剂在环境温度下通过烯丙氧基和高烯丙氧基硼烷的异构化反应生成醛衍生的烯醇硼烷。的单釜异构化/交-羟醛序列提供以良好的收率与醛的醛加成物合成 的选择性。还实现了直接使用伯烯丙基和均烯丙基醇。