(S)-2-[1-hydroxy-2-methyl-propyl]-cyclohex-2-en-1-one

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (S)-2-[1-hydroxy-2-methyl-propyl]-cyclohex-2-en-1-one
• 英文别名: (S)-2-(1-hydroxy-2-methylpropyl)cyclohex-2-enone；2-((S)-1-hydroxy-2-methylpropyl)cyclohex-2-enone；2-[(1S)-1-hydroxy-2-methylpropyl]cyclohex-2-en-1-one
• 化学式: C₁₀H₁₆O₂
• 分子量: 168.236
• InChiKey: JECYIVDZYGGHOH-JTQLQIEISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  12
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.7
• 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：

  2-环己烯-1-酮 、 异丁醛 在 三乙烯二胺 、 C₃₆H₂₆F₁₂N₄S₂ 作用下， 反应 10.0h， 以61%的产率得到(S)-2-[1-hydroxy-2-methyl-propyl]-cyclohex-2-en-1-one
  参考文献：
  名称：

  Asymmetric Morita–Baylis–Hillman reactions of 2-cyclohexen-1-one catalyzed by chiral biaryl-based bis(thiourea) organocatalysts

  摘要：

  Newly-developed bis(thiourea) 1d was found to be an efficient organocatalyst for the Morita-Baylis-Hillman reaction. High enantioselectivities were obtained in the reaction of 2-cyclohexen-1-one with both aromatic aldehydes (up to 84% ee) and aliphatic aldehydes (up to 96% ee). (C) 2011 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2011.09.064

文献信息

• Asymmetric Morita−Baylis−Hillman Reactions Catalyzed by Chiral Brønsted Acids
  作者：Nolan T. McDougal、Scott E. Schaus

  DOI：10.1021/ja037705w

  日期：2003.10.1

  Chiral BINOL-derived Brønsted acids catalyze the enantioselective asymmetric Morita-Baylis-Hillman (MBH) reaction of cyclohexenone with aldehydes. The asymmetric MBH reaction requires 2-20 mol % of the chiral Brønsted acid 2e or 2f and triethylphosphine as the nucleophilic promoter. The reaction products are obtained in good yields (39-88%) and high enantioselectivities (67-96% ee). The Brønsted-acid-catalyzed

  手性 BINOL 衍生的布朗斯台德酸催化环己烯酮与醛的对映选择性不对称 Morita-Baylis-Hillman (MBH) 反应。不对称 MBH 反应需要 2-20 mol% 的手性布朗斯台德酸 2e 或 2f 和三乙基膦作为亲核促进剂。以良好的产率 (39-88%) 和高对映选择性 (67-96% ee) 获得反应产物。布朗斯台德酸催化反应是环己烯酮与醛的高度对映选择性不对称 MBH 反应的第一个例子。
• Development of bis-thiourea-type organocatalyst for asymmetric Baylis–Hillman reaction
  作者：Yoshihiro Sohtome、Aya Tanatani、Yuichi Hashimoto、Kazuo Nagasawa

  DOI：10.1016/j.tetlet.2004.05.137

  日期：2004.7

  A new chiral bis-thiourea-type organocatalyst 2 developed for the Baylis–Hillman reaction provided a drastic rate enhancement. Allylic alcohols were obtained with up to 90% ee in the case of cyclohexanecarboxaldehyde (4i).

  为Baylis-Hillman反应开发的新型手性双硫脲型有机催化剂2极大地提高了反应速率。在环己烷甲醛（4i）的情况下，烯醇含量最高为ee的90％。
• The Development of the Asymmetric Morita—Baylis—Hillman Reaction Catalyzed by Chiral Brønsted Acids
  作者：Nolan T. McDougal、Whitney L. Trevellini、Stacy A. Rodgen、Laura T. Kliman、Scott E. Schaus

  DOI：10.1002/adsc.200404122

  日期：2004.8

  development of a chiral Brønsted acid-catalyzed asymmetric Morita–BaylisHillman (MBH) reaction of cyclohexenone with aldehydes. During the course of our studies on chiral Lewis acid-promoted MBH reactions, we discovered that chiral binaphthol-derived Brønsted acids serve as promoters of the asymmetric MBH reaction. We propose that the phosphonium enolate of cyclohexenone is stabilized via hydrogen-bonding

  该报告描述了环己烯酮与醛类手性布朗斯台德酸催化的不对称森田-贝利斯希尔曼（MBH）反应的发展。在对手性路易斯酸促进的MBH反应进行研究的过程中，我们发现手性联萘酚衍生的布朗斯台德酸可作为不对称MBH反应的促进剂。我们建议通过与二萘酚衍生的布朗斯台德酸氢键键合来稳定环己烯酮的phospho烯酸酯，从而形成手性亲核试剂。使用化学计量的PEt 3开发了一套实用而有效的条件 作为亲核助催化剂，以及联萘酚衍生的布朗斯台德酸的催化量，可以实现环己烯酮与各种脂肪族和芳香族醛的反应，产率高，对映体过量（ee最高可达96％）。
• Asymmetric Morita-Baylis-Hillman Reaction Catalyzed by Simple Amino Alcohol Derived Thioureas
  作者：Alessandra Lattanzi

  DOI：10.1055/s-2007-984882

  日期：——

  Thioureas straightforwardly derived from commercially available enantiopure amino alcohols have been found to promote the asymmetric Morita-Baylis-Hillman reaction of 2-cyclohexen-1-one and different aldehydes in the presence of triethylamine under solvent-free conditions. The corresponding allylic alcohols were obtained in good to high yields and up to 88% ee.

  直链化尿素由市售手性氨基醇衍生的化尿素，已发现能促进2-环己烯-1-酮和不同醛在无溶剂条件下，在三乙胺存在下的不对称Morita-Baylis-Hillman反应。相应的烯丙基醇以中等至高产率和高达88%的ee值获得。
• Chiral Binaphthyl-Derived Amine-Thiourea Organocatalyst-Promoted Asymmetric Morita−Baylis−Hillman Reaction
  作者：Jian Wang、Hao Li、Xinhong Yu、Liansuo Zu、Wei Wang

  DOI：10.1021/ol051822+

  日期：2005.9.1

  [reaction: see text] A new bifunctional binaphthyl-derived amine thiourea organocatalyst has been developed to promote enantioselective Morita-Baylis-Hillman reaction of cyclohexenone with a wide range of aldehydes. The process, catalyzed by the amine thiourea, affords synthetically valuable chiral allylic alcohol building blocks in high yields and high enantioselectivities.

  [反应：见正文]已开发出一种新的双官能联萘衍生的胺硫脲有机催化剂，以促进环己烯酮与多种醛的对映选择性森田-贝利斯-希尔曼反应。由胺硫脲催化的该方法以高收率和高对映选择性提供了合成上有价值的手性烯丙基醇结构单元。