N-acetylcytisine | 6018-52-6

• 分子结构分类: 有机化合物 - 生物碱及其衍生物 - 羽扇豆生物碱
• 英文名称: N-acetylcytisine
• 英文别名: N-acylcytisine；11-Acetyl-6-oxo-7,11-diazatricyclo[7.3.1.0<2,7>]trideca-2,4-diene；(1R,9S)-11-acetyl-7,11-diazatricyclo[7.3.1.02,7]trideca-2,4-dien-6-one
• CAS: 6018-52-6
• 化学式: C₁₃H₁₆N₂O₂
• 分子量: 232.282
• InChiKey: WCRIKJOQMRFVPX-WDEREUQCSA-N

物化性质

• 熔点：
  203-205 °C
• 沸点：
  506.4±49.0 °C(Predicted)
• 密度：
  1.27±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.1
• 重原子数：
  17
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.54
• 拓扑面积：
  40.6
• 氢给体数：
  0
• 氢受体数：
  2

安全信息

• 储存条件：
  存储条件：2-8°C，干燥，密封。

制备方法与用途

N-乙酰基天冬氨酸是一种生物碱，可以从苔状万年青中分离得到。

反应信息

• 作为反应物：
  描述：

  N-acetylcytisine 在 platinum(IV) oxide 、 氢气 、 溶剂黄146 作用下， 反应 26.0h， 生成 (1R,2S,9S)-11-acetyl-7,11-diazatricyclo[7.3.1.0^2,7]tridecan-6-one
  参考文献：
  名称：

  前手性膦硼烷去对称化中的新手性胺配体

  摘要：

  可以使用s -BuLi·（-）-sparteine配合物通过前手性膦硼烷的不对称化来制备P-手性膦配体。然而，该方法的局限性在于不容易获得（+）-天冬氨酸。在本文中，我们显示了另一种生物碱（-）-胱氨酸的衍生物在前手性苯基-，环己基-和叔丁基二甲基膦硼烷的去对称化中，对于（+）-天冬氨酸是有用的替代物，最多可生成手性膦硼烷92％ee。还测试了其他手性二胺，但对映选择性不如（-）-胱氨酸衍生物高。

  DOI：

  10.1016/j.tetasy.2004.09.023
• 作为产物：
  描述：

  alkaline earth salt of/the/ methylsulfuric acid 在 钯 作用下， 生成 N-acetylcytisine
  参考文献：
  名称：

  Versuche zur Synthese des Cytisins. Dehydrierung von Tetrahydro-cytisin zu Cytisin

  摘要：

  DOI：

  10.1007/bf00899864

文献信息

• 1-Acyldeoxyvasicinone salts as effective intermediate C-and N-acylating agents for alkaloids and amino acids
  作者：Kh. M. Shakhidoyatov、G. P. Genjemuratova、E. Oripov

  DOI：10.1007/s10600-006-0261-9

  日期：2006.11

  The reaction of deoxyvasicinone with acid chlorides of aliphatic (acetylbromide) and aromatic (benzoyl-, o-, p-methoxy-, p-nitrobenzoylchlorides) acids was studied. It was shown that 1-deoxyvasicinone salts were formed at room temperature; α-aroyloxymethylidenedeoxyvasicinones, in the presence of triethylamine at 80–85°C. It was found that acid chlorides cause 1-acyldeoxyvasicinone salts to transform into α-hydroxy-or α-aroyloxyarylidenedeoxyvasicinones, which indirectly confirmed their acylating properties. It was found that 1-acyldeoxyvasicinone salts were effective acylating agents for alkaloids (cytisine, 1,2-dihydrodeoxyvasicinone) and amino acids (glycine, β-alanine, α-aminobutyric acid) and can be used to acylate primary and secondary aliphatic and heterocyclic amines.

  研究了脱氧紫堇酮与脂肪族（乙酰溴）和芳香族（苯甲酰、邻、对甲氧基、对硝基苯甲酰氯）羧酸酰氯的反应。结果表明，在室温下形成1-脱氧紫堇酮盐；在三乙胺存在下，80-85°C时形成α-芳酰氧甲叉脱氧紫堇酮。研究发现，酰氯引起1-酰基脱氧紫堇酮盐转化为α-羟基或α-芳酰氧芳叉脱氧紫堇酮，间接证实了它们的酰化性质。发现1-酰基脱氧紫堇酮盐对生物碱（金雀花碱、1,2-二氢脱氧紫堇酮）和氨基酸（甘氨酸、β-丙氨酸、α-氨基丁酸）是有效的酰化剂，并可用于酰化脂肪族和杂环的一级和二级胺。
• Thionation of quinolizidine alkaloids and their derivatives via Lawesson’s reagent
  作者：Alena V. Koval’skaya、Polina R. Petrova、Dmitry O. Tsypyshev、Alexander N. Lobov、Inna P. Tsypysheva

  DOI：10.1080/14786419.2020.1868460

  日期：2022.7.18

  Abstract Direct thionation of quinolizidine alkaloids (-)-cytisine, methylcytisine, thermopsine and some of their carbonyl derivatives was realized. It was established that carrying out of the reaction in the boiling toluene with 0.5 eq. of Lawesson’s reagent (LR) is most effective for synthesis of thio analogues of methyl-, allyl-, benzylcytisine and thermopsine. It was found, that formation of thioamides

  摘要 实现了喹尼西啶生物碱(-)-金雀花碱、甲基金雀花碱、嗜热霉素及其一些羰基衍生物的直接硫化。确定在沸腾的甲苯中以0.5当量进行反应。Lawesson 试剂 (LR) 对合成甲基、烯丙基、苄基胞嘧啶和嗜热霉素的硫代类似物最有效。已发现，在起始(-)-金雀花碱的3-甲酰胺或甲基金雀花碱的2-氧代和4-氧代衍生物的情况下，优选形成硫代酰胺；并且它们的彻底硫化需要过量的 LR。结果表明，在这种方法的基础上，“金雀花碱取代的”脲和硫脲以及甲基枸橼酸与苯基马来酰亚胺的 Diels-Alder 加合物的硫代作用并不十分成功：仅发生了 2-吡啶酮核的硫代作用。
• The Enantioselective Total Synthesis of Bisquinolizidine Alkaloids: A Modular “Inside-Out” Approach
  作者：Dagmar Scharnagel、Jessica Goller、Nicklas Deibl、Wolfgang Milius、Matthias Breuning

  DOI：10.1002/anie.201712852

  日期：2018.2.23

  Bisquinolizidine alkaloids are characterized by a chiral bispidine core (3,7‐diazabicyclo[3.3.1]nonane) to which combinations of an α,N‐fused 2‐pyridone, an endo‐ or exo‐α,N‐annulated piperidin(on)e, and an exo‐allyl substituent are attached. We developed a modular “inside‐out” approach that permits access to most members of this class. Its applicability was proven in the asymmetric synthesis of 21 natural

  Bisquinolizidine生物碱的特征是手性联吡啶（3,7-二氮杂双环[3.3.1]壬烷），α，N-稠合的2-吡啶酮，内-或外-α，N-环化哌啶的组合（在）e，并连接一个外烯丙基取代基。我们开发了一种模块化的“由内而外”方法，该方法允许访问该类的大多数成员。它的适用性在21种天然双喹quin嗪生物碱的不对称合成中得到了证明，其中包括十种以上的第一对映选择性全合成。关键步骤是首次成功制备C 2的两种对映体2,4,6,8-四氧代前体的不对称化制得对称的2,6-二氧杂双吡啶，使用烯胺-溴丙烯酸策略构建α，N-稠合的2-吡啶酮，以及安装内消旋或内消旋，可选地，外环化哌啶。
• Structural features of N-acylcytisines
  作者：N. P. Abdullaev、U. S. Makhmudov、B. Tashkhodzhaev、G. Genzhemuratova、M. G. Levkovich、Kh. M. Shakhidoyatov

  DOI：10.1007/s10600-010-9495-7

  日期：2009.11

  N-Acyl cytisine derivatives were synthesized by acylation with acetic anhydride; benzoyl and o-bromo- and p-nitrobenzoyl chlorides; and crotonyl and cinnamoyl chlorides. The structures of the synthesized compounds were studied using IR, PMR, and x-ray structure analysis (XSA). PMR spectra of the N-acylcytisines in solution typically had two rotational isomers around the N12–CO bond. Conformational analysis was performed using XSA for the position of the acyl group relative to the cytisine core. Bond lengths and angles of the acyl groups involved in the conjugation were analyzed.

  乙酸酐酰化合成N-酰基金雀花碱衍生物；苯甲酰氯、邻溴苯甲酰氯和对硝基苯甲酰氯；以及巴豆酰氯和肉桂酰氯。使用IR、PMR和X射线结构分析（XSA）研究了合成化合物的结构。溶液中 N-酰基金雀花碱的 PMR 光谱通常在 N12-CO 键周围有两种旋转异构体。使用 XSA 对酰基相对于金雀花碱核心的位置进行构象分析。分析了参与共轭的酰基的键长和角度。
• Evaluation of (+)-Sparteine-like Diamines for Asymmetric Synthesis
  作者：Michael J. Dearden、Matthew J. McGrath、Peter O'Brien

  DOI：10.1021/jo049182w

  日期：2004.8.1

  Three new (+)-sparteine-like diamines were prepared from (-)-cytisine and evaluated as sparteine surrogates in the alpha-lithiation rearrangement of cyclooctene oxide and the palladium(II)/diamine catalyzed oxidative kinetic resolution of I-indanol. The new diamines exhibited opposite enantioselectivity to that observed with (-)-sparteine but increasing the steric hindrance of the N-alkyl group beyond N-Et had a detrimental effect on enantioselectivity. The optimal N-Me diamine was evaluated with much success in five other (-)-sparteine-mediated processes involving different metals (lithium, magnesium, and copper) and different types of reaction mechanisms.