<3R>-(-)-3-Methylvalerophenone | 115651-76-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: <3R>-(-)-3-Methylvalerophenone
• 英文别名: (R)-3-methyl-1-phenyl-1-penatanone；(R)-3-methyl-1-phenyl-1-pentanone；(3R)-3-methyl-1-phenyl-pentanone；(3R)-(-)-3-methylvalerophenone；1-phenyl-3-methyl pentan-1-one；3-methyl-1-phenylpentan-1-one；(3R)-3-methyl-1-phenylpentan-1-one
• CAS: 115651-76-8
• 化学式: C₁₂H₁₆O
• 分子量: 176.258
• InChiKey: LNVGEESKMXEWAR-SNVBAGLBSA-N

物化性质

• 沸点：
  253.2±9.0 °C(Predicted)
• 密度：
  0.940±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  13
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  3-methyl-1-phenyl-4-pentyn-1-one 在 RhCl(PPh₃)3 氢气 作用下， 以 乙醇 为溶剂， 20.0 ℃ 、101.33 kPa 条件下， 反应 12.0h， 生成 <3R>-(-)-3-Methylvalerophenone
  参考文献：
  名称：

  炔基链烯基甲醇的铑催化不对称重排：合成等效于烯酮的不对称共轭炔基化

  摘要：

  在羟基铑/(R)-binap 催化剂存在下，炔基烯基甲醇的炔基的不对称 1,3-重排得到 β-炔基酮以高产率和高对映选择性发生。本方法包括催化循环中关键的 β-炔基消除步骤，在合成上相当于末端炔烃与 β-取代烯酮的不对称共轭加成。

  DOI：

  10.1021/ja076346s

文献信息

• Enantioselective 1,6-Conjugate Addition of Dialkylzinc Reagents to Acyclic Dienones Catalyzed by Cu-DiPPAM Complex-Extension to Asymmetric Sequential 1,6/1,4-Conjugate Addition
  作者：Magaly Magrez-Chiquet、Marie S. T. Morin、Joanna Wencel-Delord、Sammy Drissi Amraoui、Olivier Baslé、Alexandre Alexakis、Christophe Crévisy、Marc Mauduit

  DOI：10.1002/chem.201302649

  日期：2013.10.4

  CC coupling: DiPPAM 1 and BINAP 2 ligands led to divergent behaviors in the asymmetric conjugate addition (ACA) of dialkylzinc reagents to linear aryldienones, which were applied to the development of a highly selective sequential asymmetric 1,6/1,4‐ACA process (see scheme; Tf = triflate, DBU = 1,8‐diazabicyclo[5.4.0]undec‐7‐ene).

  Ç  C偶联：DiPPAM 1和BINAP 2个配体导致的二烷基锌试剂以线性aryldienones，将其施加到一个高度选择性顺序不对称1,6- / 1,4-发展的不对称共轭加成（ACA）的发散行为ACA过程（请参阅方案； Tf =三氟甲磺酸盐，DBU = 1,8-二氮杂双环[5.4.0] undec-7-ene）。
• Steric Tuning of Silylacetylenes and Chiral Phosphine Ligands for Rhodium-Catalyzed Asymmetric Conjugate Alkynylation of Enones
  作者：Takahiro Nishimura、Xun-Xiang Guo、Nanase Uchiyama、Taisuke Katoh、Tamio Hayashi

  DOI：10.1021/ja710540s

  日期：2008.2.6

  Rhodium-catalyzed asymmetric conjugate alkynylation of α,β-unsaturated ketones giving β-alkynylketones took place in high yields with high enantioselectivity. The reaction was realized by use of (triisopropylsilyl)acetylene combined with (R)-DTBM-segphos as a chiral phosphine ligand, where the sterically bulky substituents on the silicon and phosphorus atoms suppress the alkyne dimerization.

  铑催化的 α,β-不饱和酮的不对称共轭炔基化以高产率和高对映选择性发生 β-炔基酮。该反应是通过使用（三异丙基甲硅烷基）乙炔与（R）-DTBM-segphos 结合作为手性膦配体来实现的，其中硅和磷原子上的空间庞大的取代基抑制炔二聚化。
• Enantioselective 1,4-conjugate addition of diethylzinc to (E)-alkenyl aryl ketones catalysed by Cu/DiPPAM complex
  作者：Magaly Magrez、Joanna Wencel-Delord、Christophe Crévisy、Marc Mauduit

  DOI：10.1016/j.tet.2011.05.011

  日期：2012.4

  asymmetric conjugate addition (ACA) of diethylzinc to various (E)-alkenyl aryl ketones where the aryl ring is either a phenyl group substituted by nitro, chloro or methoxy groups or not substituted, or a naphthyl group. When the conjugate addition was performed in the greener AcOEt solvent with 1 or 2 mol % of Cu(OTf)2/DiPPAM complex, moderate to good yields (45–83%) and high enantioselectivities (up to 98%)

  我们在这里报告DiPPAM - L1配体用于铜催化的二乙基锌向各种（E）-烯基芳基酮的铜催化不对称共轭加成（ACA），其中芳基环是被硝基，氯或甲氧基取代的苯基或未取代或萘基。当在具有1或2 mol％的Cu（OTf）2 / DiPPAM复合物的较绿的AcOEt溶剂中进行共轭物添加时，中度到良好的收率（45-83％）和高对映选择性（高达98％）。
• 2-Amino-1-phenyl-1,3-propanediol Derivatives. New Ligands for Asymmetric 1,4-Addition of Organozinc Reagents to Enones
  作者：Tamotsu Fujisawa、Satoru Itoh、Makoto Shimizu

  DOI：10.1246/cl.1994.1777

  日期：1994.10

  In the presence of (1S,2S)-3-benzyloxy-2-morpholino-1-phenylpropanol derived readily from (1S,2S)-2-amino-1-phenyl-1,3-propanediol and nickel acetylacetonate, diethylzinc added to α,β-unsaturated ketones to give alkylated product in high optical purity (up to 95%ee). The effects of solvents and additives and the use of such ligands as a chiral catalyst were also investigated.

  在存在(1S,2S)-3-苄氧基-2-吗啉-1-苯基丙醇的情况下，该化合物易于从(1S,2S)-2-氨基-1-苯基-1,3-丙二醇和乙酰丙酮镍盐中获得，二乙基锌添加到α,β-不饱和酮中以获得高光学纯度（最高可达95%ee）的烷基化产物。还研究了溶剂和添加剂的影响，以及将这些配体用作手性催化剂的情况。
• Efficiency of Industrially Relevant Atropisomeric Diphosphines in Copper-Catalyzed 1,4-Asymmetric Conjugate Addition of Dialkylzincs to Cyclic or Acyclic Enones or Dienones
  作者：Christophe Crévisy、Virginie Ratovelomanana-Vidal、Marc Mauduit、Marie Morin、Thomas Vives、Olivier Baslé

  DOI：10.1055/s-0034-1378813

  日期：——

  Industrially relevant atropisomeric diphosphines such as 2,2-bis(diphenylphosphino)-1,1-binaphthyl (BINAP), 6,6-bis(diphenylphosphino)-2,2,3,3-tetrahydro-5,5-bi-1,4-benzodioxin (SYNPHOS), and 5,5-bis(diphenylphosphino)-2,2,2,2-tetrafluoro-4,4-bi-1,3-benzodioxole (DIFLUORPHOS) have demonstrated their efficiency in the copper-catalyzed asymmetric conjugate addition of various dialkylzincs to -aryl enones, -aryl dienones, and cyclic dienones. Excellent 1,4- or 1,6-regioselectivities and enantioselectivities (up to 97% ee) were attained, even with challenging sterically hindered Michael acceptors.