(1S,5R,6R)-6-(4-chlorophenyl)-3-oxabicyclo[3.1.0]hexan-2-one

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 内酯类
• 英文名称: (1S,5R,6R)-6-(4-chlorophenyl)-3-oxabicyclo[3.1.0]hexan-2-one
• 化学式: C₁₁H₉ClO₂
• 分子量: 208.644
• InChiKey: CYNWEXAENUUPMJ-OPRDCNLKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  14
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  (E)-3-(p-Chlorophenyl)allyl α-diazoacetate 在 salcomine N-甲基咪唑 作用下， 以 四氢呋喃 为溶剂， 反应 24.0h， 以88%的产率得到(1S,5R,6R)-6-(4-chlorophenyl)-3-oxabicyclo[3.1.0]hexan-2-one
  参考文献：
  名称：

  Co（II）–salen催化的不对称分子内环丙烷化

  摘要：

  发现在高底物浓度下，在N-甲基咪唑存在下，旋光性Co（II）-salen配合物（5和7）催化2-烯基α-重氮乙酸酯的高对映选择性分子内环丙烷化。

  DOI：

  10.1016/s0040-4039(01)00218-0

文献信息

• α-Diazoacetates as Carbene Precursors: Metallosalen-Catalyzed Asymmetric Cyclopropanation
  作者：Tsutomu Katsuki、Tatsuya Uchida

  DOI：10.1055/s-2006-926448

  日期：2006.5

  Readily available α-diazo compounds have been shown to be efficient carbene precursors for asymmetric cyclopropanation using ruthenium(NO)-salen and cobalt-salen complexes, as catalysts. The stereoselectivity of the cyclopropanation depends on the metal ion, its valency, the structural and electronic nature of the salen ligand, and the apical ligand of the salen complex used. Both trans- and cis-selective asymmetric intermolecular cyclopropanation can be realized under mild conditions by using a suitable metallosalen complex. Furthermore, a wide range of alkenyl α-diazoacetates and the related alkenyl diazomethyl ketones undergo intramolecular cyclopropanation in a highly enantioselective manner by using various metallosalen complexes, easily prepared in a modular fashion, as catalyst.

  可 readily 获得的 α-二叠氮化合物已被证明是有效的卡宾前体，可用于使用钌(NO)-沙伦和钴-沙伦复合物作为催化剂的非对称环丙烷化反应。环丙烷化的立体选择性取决于金属离子、其价态、沙伦配体的结构和电子性质，以及所使用的沙伦复合物的顶端配体。在温和条件下，使用合适的金属沙伦复合物，可以实现顺式和反式选择性的非对称分子间环丙烷化。此外，通过使用多种金属沙伦复合物作为催化剂，广泛的烯丙基 α-二叠氮乙酸酯和相关的烯丙基二叠氮甲基酮可以以高度对映选择性的方式进行分子内环丙烷化，这些催化剂可以通过模块化方法轻松制备。
• Stereodivergent Intramolecular Cyclopropanation Enabled by Engineered Carbene Transferases
  作者：Ajay L. Chandgude、Xinkun Ren、Rudi Fasan

  DOI：10.1021/jacs.9b02700

  日期：2019.6.12

  myoglobin biocatalysts for executing asymmetric intramolecular cyclopropanations resulting in cyclopropane-fused γ-lactones, which are key motifs found in many bioactive molecules. Using this strategy, a broad range of allyl diazoacetate substrates were efficiently cyclized in high yields with up to 99% enantiomeric excess. Upon remodeling of the active site via protein engineering, myoglobin variants

  我们报告了用于执行不对称分子内环丙烷化的工程化肌红蛋白生物催化剂的开发，导致环丙烷融合的 γ-内酯，这是许多生物活性分子中发现的关键基序。使用这种策略，广泛的重氮乙酸烯丙酯底物以高产率有效环化，对映体过量高达 99%。通过蛋白质工程改造活性位点后，还获得了具有立体发散选择性的肌红蛋白变体。与全细胞转化相结合，这些生物催化剂能够实现关键中间体的克级组装，用于合成杀虫剂氯菊酯和其他天然产物。酶促产生的环丙基-γ-内酯可以进一步加工以提供各种对映体纯的三取代环丙烷。
• Intramolecular Asymmetric Cyclopropanation with (Nitroso)(salen)ruthenium(II) Complexes as Catalysts
  作者：Biswajit Saha、Tatsuya Uchida、Tsutomu Katsuki

  DOI：10.1055/s-2001-9733

  日期：——

  Intramolecular cyclopropanation of (E)-2-alkenyl-α-diazoacetates was carried out with good to high enantioselectivity by using (nitroso)(salen)ruthenium(II) complexes as catalysts under photo-irradiation.

  (E)-2-烯基-α-重氮乙酸酯的分子内环丙烷化反应在光照射下使用(亚硝基)(salen)钌(II)配合物作为催化剂进行，具有良好至高的对映选择性。
• Chiral Bis(pyridylimino)isoindoles: A Highly Modular Class of Pincer Ligands for Enantioselective Catalysis
  作者：Björn K. Langlotz、Hubert Wadepohl、Lutz H. Gade

  DOI：10.1002/anie.200801150

  日期：2008.6.9
• Asymmetric intramolecular cyclopropanation of diazo compounds with metallosalen complexes as catalyst: structural tuning of salen ligand
  作者：Biswajit Saha、Tatsuya Uchida、Tsutomu Katsuki

  DOI：10.1016/s0957-4166(03)00167-8

  日期：2003.4

  Intramolecular cyclopropanation of alkenyl alpha-diazoacetates and alkenyl diazomethyl ketones was examined by using optically active (ON+)Ru(11)(salen) and Co(II)(salen) complexes as catalysts. For the cyclization of 2-alkenyl alpha-diazoacetates, Co(II)(salen) complexes 9 and 10 were found to be superior catalysts to the corresponding (ON+)Ru(11)(salen) complexes 4 and 5. On the other hand, (ON+)Ru(II)(salen) complex 2 was found to be the catalyst of choice for the cyclization of 3-alkenyl diazomethyl ketones, and complex 4 was found to be a good catalyst for the cyclization of (E)-4-alkenyl diazomethyl ketones. The present study demonstrates that metallosalen complexes, especially optically active (ON+)Ru(II)(salen) and Co(11)(salen) complexes, can serve as efficient catalysts for the cyclization of alkenyl diazocarbonyl compounds, if a suitable salen ligand is used as the chiral auxiliary. (C) 2003 Elsevier Science Ltd. All rights reserved.