(R)-4-methyl-4-phenyl-2-cyclopentenone

• 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: (R)-4-methyl-4-phenyl-2-cyclopentenone
• 英文别名: (4R)-4-methyl-4-phenyl-2-cyclopenten-1-one；(4R)-4-methyl-4-phenylcyclopent-2-en-1-one
• 化学式: C₁₂H₁₂O
• 分子量: 172.227
• InChiKey: SXHZXSGKGZNPBR-LBPRGKRZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  13
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.25
• 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：

  4-环戊烯-1,3-二酮 在 重氮甲烷 、 三氟化硼乙醚 、 对甲苯磺酸 作用下， 以 二氯甲烷 为溶剂， 25.0~400.0 ℃ 、700.0 MPa 条件下， 反应 24.0h， 生成 (R)-4-methyl-4-phenyl-2-cyclopentenone
  参考文献：
  名称：

  Pure enantiomers from simple, symmetric dienophiles

  摘要：

  Starting from p-benzoquinone or 2-cyclopentene-1, 4-dione as dienophiles and the enantiomerically pure dienes 1a and 1b, high pressure cycloadditions led to chiral adducts. These were transformed in a regioselective manner to generate well defined stereogenic centres. A remarkably efficient electron density directed regioselectivity was discovered with 18c and 18d.

  DOI：

  10.1016/0957-4166(94)80092-8

文献信息

• Asymmetric synthesis of 4,4-disubstituted 2-cyclopentenones from optically active 1-chlorovinyl p-tolyl sulfoxides and cyanomethyllithium with formation of a quaternary chiral center
  作者：Tsuyoshi Satoh、Masaaki Yoshida、Hiroyuki Ota

  DOI：10.1016/s0040-4039(01)02034-2

  日期：2001.12

  Treatment of optically active 1-chlorovinyl p-tolyl sulfoxides having two different substituents at the 2-position, which were synthesized from unsymmetrical ketones and (R)-(−)-chloromethyl p-tolyl sulfoxide in three steps, with cyanomethyllithium gave optically active 2-amino-1-cyano-5,5-disubstituted-1,3-cyclopentadienes with very high asymmetric induction from the sulfoxide chiral center. The products

  光学活性的1-氯乙烯基的治疗p具有在2-位，这是从不对称酮合成和两个不同的取代基间-甲苯基砜（[R ）- （ - ） -氯甲基p -甲苯基砜在三个步骤中，与cyanomethyllithium得到光学活性来自亚砜手性中心的非对称诱导非常高的2-氨基-1-氰基-5,5-二取代-1,3-环戊二烯。通过与磷酸在乙酸中加热，将产物转化为对映体纯的4，4-二取代的2-环戊烯酮。
• A novel method for the asymmetric synthesis of 4,4-disubstituted 2-cyclopentenones from optically active 1-chlorovinyl p-tolyl sulfoxides and its application to the asymmetric total synthesis of (+)-α-cuparenone
  作者：Tsuyoshi Satoh、Masaaki Yoshida、Yasuhiro Takahashi、Hiroyuki Ota

  DOI：10.1016/s0957-4166(02)00797-8

  日期：2003.1

  of the 1-chlorovinyl p-tolyl sulfoxides with cyanomethyllithium at −78°C to room temperature gave optically active 2-amino-1-cyano-5,5-disubstituted-1,3-cyclopentadienes in high yields with very high asymmetric induction from the stereogenic center of the sulfoxide moiety. A mechanism for the asymmetric induction is proposed. The products were treated with phosphoric acid in acetic acid at reflux temperature

  对映体纯1-氯乙烯基p具有在2-位上有两个不同的取代基间-甲苯基砜从不对称酮合成和（- [R ）- （ - ） -氯甲基p -甲苯基砜中的三个步骤。1-氯乙烯基p的处理-甲苯基亚砜与氰基甲基锂在-78°C至室温下以高收率得到光学活性的2-氨基-1-氰基-5,5-二取代-1,3-环戊二烯，并从亚砜的立体异构中心非常不对称地诱导部分。提出了一种非对称感应的机制。将产物在回流温度下用磷酸的乙酸溶液处理，以良好的产率得到对映体纯的4，4-二取代的2-环戊烯酮。作为该合成方法的一种应用，描述了由甲基4-甲基苯基酮进行的相对短的（七个步骤）全不对称合成（+）-α-cuparenone。
• Pure enantiomers from simple, symmetric dienophiles
  作者：Pierre Riviere、Antony Mauvais、Ekkehard Winterfeldt

  DOI：10.1016/0957-4166(94)80092-8

  日期：1994.9

  Starting from p-benzoquinone or 2-cyclopentene-1, 4-dione as dienophiles and the enantiomerically pure dienes 1a and 1b, high pressure cycloadditions led to chiral adducts. These were transformed in a regioselective manner to generate well defined stereogenic centres. A remarkably efficient electron density directed regioselectivity was discovered with 18c and 18d.