2-[(4-chlorophenyl)hydroxymethyl]cyclohex-2-enone

• 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: 2-[(4-chlorophenyl)hydroxymethyl]cyclohex-2-enone
• 英文别名: 2-[(R)-(4-chlorophenyl)-hydroxymethyl]cyclohex-2-en-1-one
• 化学式: C₁₃H₁₃ClO₂
• 分子量: 236.698
• InChiKey: LGOVISIADUTJQV-CYBMUJFWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  16
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.31
• 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 、 4-氯苯甲醛 在 enzyme BH_32.14 作用下， 以 aq. phosphate buffer 为溶剂， 以89%的产率得到
  参考文献：
  名称：

  为 Morita-Baylis-Hillman 反应设计一种高效的对映选择性酶

  摘要：

  计算设计和定向进化的结合可以提供一种通用策略来创建具有新功能的酶。到目前为止，这种方法已经为少数模型反应提供了酶。在这里，我们表明可以将新的催化机制设计到蛋白质中以加速更具挑战性的化学转化。原始设计的进化优化为 Morita-Baylis-Hillman (MBH) 反应提供了一种高效的对映选择性酶 (BH32.14)。BH32.14 适用于制备规模的转化，接受范围广泛的醛和烯酮偶联伙伴，并能够促进二醛的选择性单官能化。晶体学、生物化学和计算研究表明 BH32。14 通过复杂的催化机制运作，该机制包括 His23 亲核试剂与明智定位的 Arg124 配对。这种催化精氨酸在构象状态之间穿梭以稳定多个氧阴离子中间体，并作为特殊双齿氢键催化剂（例如，硫脲）的遗传编码替代物。这项研究表明，可以从头开始构建精心设计的催化装置，以促进在自然界中未观察到的要求苛刻的多步过程。

  DOI：

  10.1038/s41557-021-00833-9

文献信息

• Method for Performing Aldol Reaction in Water
  申请人：Kobayashi Shu

  公开号：US20070238902A1

  公开（公告）日：2007-10-11

  An aldol reaction in an aqueous solution between an aldehyde represented by the following formula (I): R—CHO  (I) (wherein R is a hydrocarbon group which may have an substituent), and a silicon enolate represented by the following formula (II): (wherein R 1 and R 2 are a hydrogen atom or an aliphatic hydrocarbon group, at least one of them being an aliphatic hydrocarbon group; and R 3 is a substituent selected from the group consisting of an aliphatic hydrocarbon group, an aromatic hydrocarbon group and a sulfur-containing substituent, wherein R 2 and R 3 may be combined with each other to form a ring) is performed so as to generate diastereoselectivity by using FeCl 3 , which is a low-cost Lewis acid, and a surfactant.

  在水溶液中进行的醛缩反应，其中一个醛以以下式表示：R—CHO (I)（其中R是一个可能带有取代基的碳氢基团），另一个是以以下式表示的硅烯醇：（式中R1和R2是氢原子或脂肪烃基团，至少一个是脂肪烃基团；R3是从脂肪烃基团、芳香烃基团和含硫取代基组成的群中选择的取代基，其中R2和R3可以结合在一起形成环），通过使用FeCl3（一种低成本的Lewis酸）和表面活性剂来产生对映选择性。
• Comparison between Chemoenzymatic and Bienzymatic Cascades Leading to Morita–Baylis–Hillman Adducts
  作者：Yinuo Li、Cuiyu Bao、Zhoutong Sun、Wuyuan Zhang、Bo Yuan

  DOI：10.1002/cctc.202201621

  日期：——

  Chemoenzymatic and bienzymatic cascades: We herein present three cascade routes to produce MBH adducts and compare the key advantages and challenges of the chemoenzymatic and bienzymatic methodologies.

  化学酶促和双酶促级联：我们在此提出了三种级联途径来生产 MBH 加合物，并比较了化学酶促和双酶促方法的主要优势和挑战。
• Asymmetric Morita–Baylis–Hillman reactions of 2-cyclohexen-1-one catalyzed by chiral biaryl-based bis(thiourea) organocatalysts
  作者：Yuki Nakayama、Takashi Gotanda、Katsuji Ito

  DOI：10.1016/j.tetlet.2011.09.064

  日期：2011.11

  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.
• Asymmetric Morita-Baylis-Hillman Reaction of Arylaldehydes with 2-Cyclohexen-1-one Catalyzed by Chiral Bis(Thio)urea and DABCO
  作者：Min Shi、Xu-Guang Liu

  DOI：10.1021/ol7028806

  日期：2008.3.1

  Novel bis(thio)urea organocatalysts were synthesized from axially chiral (R)-(-)-5,5',6,6',7,7',8,8'-octahydro-1,1'-binaphthyl-2,2'-diamine (H-8-BINAM), and their catalytic abilities have been examined in the Morita-Baylis-Hillman reaction of 2-cyclohexen-1-one or 2-cyclopenten-1-one with a wide range of aromatic aldehydes in combination with DABCO. The best result was achieved in the reaction of 3-fluorobenzaldehyde with 2-cyclohexen-1-one to give the desired Morita-Baylis-Hillman product in 79% yield and 88% ee.
• Asymmetric Morita–Baylis–Hillman reaction catalyzed by pepsin
  作者：Jing-Wen Xue、Jian Song、Ian C.K. Manion、Yan-Hong He、Zhi Guan

  DOI：10.1016/j.molcatb.2015.12.002

  日期：2016.2

  Pepsin from porcine gastric mucous shown catalytic promiscuity was first discovered to catalyze the Morita-Baylis-Hillman (MBH) reaction between aromatic aldehydes with 2-cyclohexen-1-one or 2-cyclopenten-i-one in a two-phase medium of phosphate buffer/cyclohexane in the presence of 1,4-diazabicyclo[2.2.2]octane (DABCO). The best results of the corresponding MBH products up to 77% yield and 38% ee were achieved. (C) 2015 Elsevier B.V. All rights reserved.