(4R)-methyl 2-hydroxy-7,7-dimethyl-5-oxo-4-phenyl-3,4,5,6,7,8-hexahydro-2H-chromene-2-carboxylate | 1234199-85-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并吡喃
• 英文名称: (4R)-methyl 2-hydroxy-7,7-dimethyl-5-oxo-4-phenyl-3,4,5,6,7,8-hexahydro-2H-chromene-2-carboxylate
• 英文别名: methyl (4R)-2-hydroxy-7,7-dimethyl-5-oxo-4-phenyl-3,4,6,8-tetrahydrochromene-2-carboxylate
• CAS: 1234199-85-9
• 化学式: C₁₉H₂₂O₅
• 分子量: 330.381
• InChiKey: SYNLQFBQIZBCJW-BSOCMFCZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  24
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.47
• 拓扑面积：
  72.8
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为产物：
  描述：

  3-羟基-5,5-二甲基环己-2-烯-1-酮 、 2-氧代-4-苯基-3-丁酸甲酯 在 C₂₉H₂₉F₆N₃OS 作用下， 以 乙醚 为溶剂， 反应 5.0h， 以99%的产率得到(4R)-methyl 2-hydroxy-7,7-dimethyl-5-oxo-4-phenyl-3,4,5,6,7,8-hexahydro-2H-chromene-2-carboxylate
  参考文献：
  名称：

  环状1,3-二羰基化合物对β，γ-不饱和α-酮酯的高对映选择性迈克尔加成

  摘要：

  提出了由氨基酸衍生的硫脲-叔胺催化剂催化的环状1,3-二羰基化合物对β，γ-不饱和α-酮酯的高对映选择性迈克尔加成反应。使用5 mol％的新型酪氨酸衍生的硫脲催化剂，可在极短的反应时间内，在非常温和的条件下，以优异的收率（高达99％）和高达96％ee获得一系列手性香豆素衍生物。

  DOI：

  10.1002/adsc.201000045

文献信息

• Highly Enantioselective Conjugate Addition of Cyclic Diketones to β,γ-Unsaturated α-Ketoesters Catalyzed by an N,N′-Dioxide-Cu(OTf)2 Complex
  作者：Zhenhua Dong、Juhua Feng、Xuan Fu、Xiaohua Liu、Lili Lin、Xiaoming Feng

  DOI：10.1002/chem.201002687

  日期：2011.1.24

  Copper‐catalyzed conjugate addition: A highly enantioselective conjugate addition of cyclic diketones to β,γ‐unsaturated α‐ketoesters was achieved by using a two‐carbon‐linked N,N′‐dioxide‐Cu(OTf)2 complex. Excellent yields (up to 99 %) and enantioselectivities (up to 99 % ee) were obtained with 2 mol % catalyst loading (see scheme). By using this method, adducts could be easily transformed into hexahydroquinolines

  铜催化的共轭物加成：通过使用两个碳连接的N，N'-二氧化物-Cu（OTf）2络合物，将环状二酮高度对映选择性共轭加成到β，γ-不饱和的α-酮酸酯上。在催化剂负载量为2 mol％的情况下，可获得极佳的收率（高达99％）和对映选择性（高达99％  ee）（请参阅方案）。通过使用这种方法，加合物可以很容易地转化为六氢喹啉。反应也可以按比例放大至克量，而不会损失收率或对映选择性。
• <i>trans</i>-1,2-Diaminocyclohexane-based sulfonamides as effective hydrogen-bonding organocatalysts for asymmetric Michael–hemiacetalization reaction
  作者：Maciej Dajek、Rafał Kowalczyk、Przemysław J. Boratyński

  DOI：10.1039/c8cy01199k

  日期：——

  bifunctional monosulfonamide derivative of DACH was an effective catalyst for Michael addition–hemiacetalization reactions, providing products with ees exceeding 99% under optimized conditions. High enantioselectivities were achieved with just 0.2% mol catalyst loading. The sulfonamide outperformed analogous thiourea and squaramide-based organocatalysts.

  一种易于获得的DACH双官能单磺酰胺衍生物是迈克尔加成-半缩醛化反应的有效催化剂，可在优化条件下提供ee超过99％的产品。仅催化剂负载量为0.2％mol时，就可以实现高对映选择性。磺酰胺的性能优于类似的硫脲和方胺基有机催化剂。
• Dinuclear zinc catalyzed asymmetric tandem Michael addition/acetalization reactions of cyclic diketones and β,γ-unsaturated α-ketoesters
  作者：Xixi Song、Jing Liu、Meng-Meng Liu、Xi Wang、Zhao-Fei Zhang、Min-Can Wang、Junbiao Chang

  DOI：10.1016/j.tet.2014.06.109

  日期：2014.9

  The dinuclear zinc–ProPhenol complex is applied as efficient catalyst in the highly stereoselective tandem Michael addition/acetalization reactions of cyclic 1,3-diketones and β,γ-unsaturated α-ketoesters. A variety of substrates are well-tolerated, and a broad range of synthetically and pharmaceutically useful chiral chromene derivatives are directly produced in good yields of up to 96% and good

  双核锌-ProPhenol配合物在环状1,3-二酮和β，γ-不饱和α-酮酸酯的高度立体选择性串联迈克尔加成/缩醛反应中用作有效的催化剂。多种底物具有良好的耐受性，并且直接以高达96％的高收率和高达96％ee的良好对映选择性直接生产了广泛的合成和药学上有用的手性色烯衍生物。
• Enzyme-Catalyzed Cascade Michael/Cyclization Reaction for the Synthesis of 3,4-Dihydropyran Derivatives by Using a Protease
  作者：Xuan Ding、Xue-Dong Zhang、Chun-Lin Dong、Zhi Guan、Yan-Hong He

  DOI：10.1007/s10562-017-2275-2

  日期：2018.2

  the Michael/cyclization reaction between dimedone and aryl or alkyl substituted α,β-unsaturated ketones or ester for the synthesis of 3,4-dihydropyran derivatives. The products were obtained in moderate to excellent yields (46–95%) with certain enantioselectivities (up to 18% ee) for 27 examples. This process afforded a potential biocatalytic approach as alternative to chemical synthesis for 3,4-dihydropyran

  摘要 灰色链霉菌 (SGP) 蛋白酶作为一种可持续的生物催化剂，已成功应用于二甲酮与芳基或烷基取代的 α,β-不饱和酮或酯之间的迈克尔/环化反应，以合成 3,4-二氢吡喃衍生物。对于 27 个实例，以中等至极好的收率（46-95%）获得了具有某些对映选择性（高达 18% ee）的产物。该过程提供了一种潜在的生物催化方法，可替代 3,4-二氢吡喃衍生物的化学合成。Graphical AbstractProtease from Streptomyces griseus (SGP) 用作合成 3,4-二氢吡喃衍生物的迈克尔加成/环化反应的催化剂
• Amine-Squaramide Catalyzed Asymmetric Michael Addition of Cyclic Diketones and β,γ-unsaturated α-keto Esters
  作者：Zhi-Wei Ma、Zhi-Jing Liu、Xiao-Pei Chen、Chuan-Chuan Wang、Jun-Tao Liu、Jing-Chao Tao

  DOI：10.2174/1570178619666220314152530

  日期：2022.11

  applied to catalyze the asymmetric Michael addition between cyclic diketones and β,γ-unsaturated α-ketoesters. The catalyst system performed well with a low catalyst loading of 1 mol% under mild reaction conditions. A series of synthetically and pharmaceutically useful chiral bicyclic compounds were obtained with both high yields (up to 97%) and excellent enantioselectivities (up to 97% ee).

  【摘要】：成功开发了一种新型叔胺方酰胺,并应用于催化环状二酮与β,γ-不饱和α-酮酯之间的不对称迈克尔加成反应。该催化剂体系在温和的反应条件下以 1 mol% 的低催化剂负载量表现良好。以高产率（高达 97%）和优异的对映选择性（高达 97% ee）获得了一系列合成和药学有用的手性双环化合物。