(1R,2R)-1-(2-aminocyclohexyl)-3-[(S)-1-phenylethyl]thiourea | 313695-77-1

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: (1R,2R)-1-(2-aminocyclohexyl)-3-[(S)-1-phenylethyl]thiourea
• 英文别名: 1-[(1R,2R)-2-aminocyclohexyl]-3-[(S)-1-phenylethyl]thiourea；1-[(1R,2R)-2-aminocyclohexyl]-3-[(1S)-1-phenylethyl]thiourea
• CAS: 313695-77-1
• 化学式: C₁₅H₂₃N₃S
• 分子量: 277.434
• InChiKey: OLIBTEDVASBVGX-IACUBPJLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  19
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.53
• 拓扑面积：
  82.2
• 氢给体数：
  3
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (1R,2R)-1-(2-aminocyclohexyl)-3-[(S)-1-phenylethyl]thiourea 在 2-氯-1,3-二甲基氯化咪唑啉 、 三乙胺 作用下， 以 二氯甲烷 、 乙腈 为溶剂， 生成 (1R,6R)-7-benzoyl-8-[(S)-1-phenylethylimino]-7,9-diazabicyclo[4.3.0]nonane
  参考文献：
  名称：

  Modified Guanidines as Potential Chiral Superbases. 2. Preparation of 1,3-Unsubstituted and 1-Substituted 2-Iminoimidazolidine Derivatives and a Related Guanidine by the 2-Chloro-1,3-dimethylimidazolinium Chloride-Induced Cyclization of Thioureas

  摘要：

  Simple preparation methods for modified guanidines were explored for new chiral superbases, Thus, (4S,5S)-4,5-diphenyl- and diastereomeric cyclohexane-fused 2-iminoimidazolidines were prepared from (1S,2S)-1,2-diphenylethylenediamine and (1R,2R)- or (1S,2S)-1,2-diaminocyclohexanes through cyclization of protected thiourea intermediates with 2-chloro-1,3-dimethylimidazolinium chloride (DMC) as a key reaction. In the (4S,SS)-4,5-diphenyl series 1-methyl-2-iminoimidazolidines and 2-diethylaminoimidazoline were also prepared as related guanidines.

  DOI：

  10.1021/jo000745n
• 作为产物：
  描述：

  triethylammonium (S)-N-(1-phenylethyl)dithiocarbamate 在 2-氯-1,3-二甲基氯化咪唑啉 作用下， 以 二氯甲烷 为溶剂， 反应 121.0h， 生成 (1R,2R)-1-(2-aminocyclohexyl)-3-[(S)-1-phenylethyl]thiourea
  参考文献：
  名称：

  Modified Guanidines as Potential Chiral Superbases. 2. Preparation of 1,3-Unsubstituted and 1-Substituted 2-Iminoimidazolidine Derivatives and a Related Guanidine by the 2-Chloro-1,3-dimethylimidazolinium Chloride-Induced Cyclization of Thioureas

  摘要：

  Simple preparation methods for modified guanidines were explored for new chiral superbases, Thus, (4S,5S)-4,5-diphenyl- and diastereomeric cyclohexane-fused 2-iminoimidazolidines were prepared from (1S,2S)-1,2-diphenylethylenediamine and (1R,2R)- or (1S,2S)-1,2-diaminocyclohexanes through cyclization of protected thiourea intermediates with 2-chloro-1,3-dimethylimidazolinium chloride (DMC) as a key reaction. In the (4S,SS)-4,5-diphenyl series 1-methyl-2-iminoimidazolidines and 2-diethylaminoimidazoline were also prepared as related guanidines.

  DOI：

  10.1021/jo000745n
• 作为试剂：
  描述：

  β-硝基苯乙烯 、 苯乙酮 在 (1R,2R)-1-(2-aminocyclohexyl)-3-[(S)-1-phenylethyl]thiourea 、 对硝基苯甲酸 作用下， 以 二氯甲烷 为溶剂， 反应 72.25h， 以91%的产率得到(S)-4-nitro-1,3-diphenylbutan-1-one
  参考文献：
  名称：

  双功能硫脲催化芳香酮对硝基烯烃的对映选择性迈克尔加成和机理洞察

  摘要：

  在手性双官能伯胺-硫脲催化剂和4-硝基苯甲酸作为助催化剂存在下，芳香酮与硝基烯烃的高度对映选择性迈克尔反应；以优异的对映选择性（高达 99 % ee）和产率（高达 98 %）获得了相应的加合物。迈克尔反应的催化机理通过对反应中间体的 ESI-MS 检测和硫脲和硝基烯烃之间氢键的 1 H NMR 检测得到证实。DFT 计算表明，硫脲的手性部分显着影响了加合物的产率和对映选择性，这与观察到的实验结果相对应。

  DOI：

  10.1002/ejoc.200900932

文献信息

• The effect of chiral <i>N</i>-substituents with methyl or trifluoromethyl groups on the catalytic performance of mono- and bifunctional thioureas
  作者：Josué Vazquez-Chavez、Socorro Luna-Morales、Diego A. Cruz-Aguilar、Howard Díaz-Salazar、Wilmer E. Vallejo Narváez、Rodrigo S. Silva-Gutiérrez、Simón Hernández-Ortega、Tomás Rocha-Rinza、Marcos Hernández-Rodríguez

  DOI：10.1039/c9ob01893j

  日期：——

  thiourea organocatalysts that incorporate a chiral group which includes a trifluoromethyl moiety and contrasted their performance with non-fluorinated analogs. The comparison between such systems allows the direct study of the NH acidity of a thiourea bonded to an aliphatic substituent. In principle, –CF3 systems feature an enhanced hydrogen bond (HB) donor capacity that is undoubtedly beneficial for

  我们评估了含有手性基团（包括三氟甲基部分）的硫脲有机催化剂，并将其性能与非氟化类似物进行了对比。这些系统之间的比较允许直接研究与脂族取代基键合的硫脲的NH酸度。原则上，–CF 3系统具有增强的氢键（HB）供体容量，这无疑有利于应用于Baylis-Hillman反应的HB催化。我们发现，像Schreiner的硫脲一样，在两个氮原子上都被该基团取代的硫脲可加速该反应。另一方面，我们在双功能催化剂（硫脲-伯胺）促进的反应中观察到了不同的行为。在异丁醛向亚苄基丙酮酸甲酯的迈克尔加成反应中，–CF 3含催化剂的性能优于–CH 3体系，而将共轭物添加至N-苯基马来酰亚胺则表现出相反的行为。过渡态的理论计算表明，氟化和非氟化化合物中的苯乙基与亲电试剂具有不同种类的相互作用。这些相互作用导致亲电试剂的不同排列，从而导致催化剂的选择性。因此，不能一概而论，在所有情况下，NH的酸度都与催化剂的性能有关，特别是
• Synthesis and antiviral bioactivities of novel chiral bis-thiourea-type derivatives containing α-aminophosphonate moiety
  作者：Xuan Yang、BaoAn Song、LinHong Jin、Xue Wei、S. Pinaki Bhadury、XiangYang Li、Song Yang、DeYu Hu

  DOI：10.1007/s11426-010-4179-5

  日期：2011.1

  and substituted isothiocyanates (9a–d), chiral bis-thiourea derivatives containing α-aminophosphonate moiety 10a–l were prepared and completely characterized by elemental analysis, physical and spectral (IR, 1H NMR, 13C NMR, 31P NMR) data. The results of bioassay revealed that compounds 10a and 10e possessed appreciable curative bioactivities on cucumber mosaic virus (CMV) at 0.5 mg/mL in vivo (inhibitory

  从1开始- （（1 - [R，2 - [R）-2-氨基环己基）-3-取代的硫脲（3A-C ）和取代的异硫氰酸酯（图9a-d ），手性双-硫脲的含α-氨基膦基团的衍生物10A-1是制备并通过元素分析，物理和光谱（IR，1 H NMR，13 C NMR，31 P NMR）数据完全表征。生物测定的结果表明，化合物10a和10e在体内对黄瓜花叶病毒（CMV）具有0.5 mg / mL的显着治愈性生物活性。（抑制率分别为60.3％，64.8％）和烟草花叶病毒（TMV）在体内浓度为0.5 mg / mL （抑制率分别为50.3％，50.8％），与标准参考文献显示的值（58.7％）相近）和市售产品宁南霉素（56.3％）。手性化合物10e显示出比宁南霉素（EC 50 = 0.201mg / mL）更强的抗CMV抗病毒活性（EC 50 = 0.149 mg / mL）。
• Asymmetric conjugate addition of carbonyl compounds to nitroalkenes catalyzed by chiral bifunctional thioureas
  作者：Xue-jing Zhang、Sheng-ping Liu、Jin-hua Lao、Guang-jian Du、Ming Yan、Albert S.C. Chan

  DOI：10.1016/j.tetasy.2009.06.003

  日期：2009.7

  Readily available chiral thioureas derived from cyclohexane-1,2-diamine were prepared and found to be highly effective organocatalysts for the conjugate addition of aldehydes and ketones to nitroalkenes. Excellent enantioselectivities and yields were obtained for a variety of aryl and heteroaryl nitroalkenes. The base additives are essential for good yields and excellent enantioselectivities in this

  制备了易于获得的衍生自环己烷-1，2-二胺的手性硫脲，并发现其是将醛和酮共轭加成至硝基烯烃的高效有机催化剂。对于各种芳基和杂芳基硝基烯烃，获得了优异的对映选择性和收率。在这种转化中，基础添加剂对于获得高收率和出色的对映选择性至关重要。基于新的实验证据，提出了一种改进的催化机理，以使基础添加剂的重要作用合理化。
• Modified Guanidines as Potential Chiral Superbases. 2. Preparation of 1,3-Unsubstituted and 1-Substituted 2-Iminoimidazolidine Derivatives and a Related Guanidine by the 2-Chloro-1,3-dimethylimidazolinium Chloride-Induced Cyclization of Thioureas
  作者：Toshio Isobe、Keiko Fukuda、Tatsuhiro Tokunaga、Hiroko Seki、Kentaro Yamaguchi、Tsutomu Ishikawa

  DOI：10.1021/jo000745n

  日期：2000.11.1

  Simple preparation methods for modified guanidines were explored for new chiral superbases, Thus, (4S,5S)-4,5-diphenyl- and diastereomeric cyclohexane-fused 2-iminoimidazolidines were prepared from (1S,2S)-1,2-diphenylethylenediamine and (1R,2R)- or (1S,2S)-1,2-diaminocyclohexanes through cyclization of protected thiourea intermediates with 2-chloro-1,3-dimethylimidazolinium chloride (DMC) as a key reaction. In the (4S,SS)-4,5-diphenyl series 1-methyl-2-iminoimidazolidines and 2-diethylaminoimidazoline were also prepared as related guanidines.