(-)-(1S,2S)-pseudoephenamine

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 二苯乙烯类
• 英文名称: (-)-(1S,2S)-pseudoephenamine
• 英文别名: (-)-pseudoephenamine；(1S,2S)-2-(Methylamino)-1,2-diphenylethan-1-ol；(1S,2S)-2-(methylamino)-1,2-diphenylethanol
• 化学式: C₁₅H₁₇NO
• 分子量: 227.306
• InChiKey: BLDFSDCBQJUWFG-GJZGRUSLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  17
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  32.3
• 氢给体数：
  2
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (-)-(1S,2S)-pseudoephenamine 在 lithium aluminium tetrahydride 、 溶剂黄146 、 sodium nitrite 作用下， 以 四氢呋喃 、 乙醚 、 乙醇 、 水 为溶剂， 生成 (1S,2S)-2-(1-methylhydrazino)-1,2-diphenylethanol fumarate
  参考文献：
  名称：

  Novel Hydrazine Molecules as Tools To Understand the Flexibility of Vascular Adhesion Protein-1 Ligand-Binding Site: Toward More Selective Inhibitors

  摘要：

  Vascular adhesion protein-1 (VAP-1) belongs to a family of amine oxidases. It plays a role in leukocyte trafficking and in amine compound metabolism. VAP-1 is linked to various diseases, such as Alzheimer's disease, psoriasis, depression, diabetes, and obesity. Accordingly, selective inhibitors of VAP-1 could potentially be used to treat those diseases. In this study, eight novel VAP-1 hydrazine derivatives were synthesized and their VAP-1 and monoamine oxidase (MAO) inhibition ability was determined in vitro. MD simulations of VAP-1 with these new molecules reveal that the VAP-1 ligand-binding pocket is flexible and capable of fitting substantially larger ligands than was previously believed. The increase in the size of the VAP-1 ligands, together with the methylation of the secondary nitrogen atom of the hydrazine moiety, improves the VAP-1 selectivity over MAO.

  DOI：

  10.1021/jm200059p
• 作为产物：
  描述：

  (1R,2S)-1,2-diphenyl-2-formamidoethanol 在 lithium aluminium tetrahydride 作用下， 以 四氢呋喃 、 乙醚 为溶剂， 以67%的产率得到(-)-(1S,2S)-pseudoephenamine
  参考文献：
  名称：

  束缚的磺酰胺将未活化的醇立体转化。

  摘要：

  未活化醇的直接催化取代仍然是有机合成的未开发领域。此外，具有可预测的立体结果的这种困难的亲电试剂的催化活化提出了甚至更大的挑战。本文描述了一种简单的铁基催化剂体系，该体系提供了仲和叔醇向磺酰胺的温和，直接的转化。从富含对映体的醇开始，分子内变体进行立体转化以产生富含对映体的2-和2,2-取代的吡咯烷和二氢吲哚，而无需事先衍生化醇或溶剂化条件。

  DOI：

  10.1002/anie.201812894

文献信息

• Pseudoephedrine-Directed Asymmetric α-Arylation of α-Amino Acid Derivatives
  作者：Rachel C. Atkinson、Fernando Fernández-Nieto、Josep Mas Roselló、Jonathan Clayden

  DOI：10.1002/anie.201502569

  日期：2015.7.27

  Available α‐amino acids undergo arylation at their α position in an enantioselective manner on treatment with base of N′‐aryl urea derivatives ligated to pseudoephedrine as a chiral auxiliary. In situ silylation and enolization induces diastereoselective migration of the N′‐aryl group to the α position of the amino acid, followed by ring closure to a hydantoin with concomitant explulsion of the recyclable

  可用的α-氨基酸在与连接到假麻黄碱的N'-芳基尿素衍生物的碱作为手性助剂的处理下，以对映选择性的方式在其α位进行芳基化。原位甲硅烷基化和烯醇化诱导N'-芳基向非对映选择性迁移至氨基酸的α位置，随后闭环至乙内酰脲，同时伴随着可回收助剂的爆炸。乙内酰脲产物的水解提供了季氨基酸的衍生物。芳基化避免使用重金属添加剂，并且成功地用于一系列氨基酸和具有不同电子特性的芳基环。
• Pseudoephenamine: A Practical Chiral Auxiliary for Asymmetric Synthesis
  作者：Marvin R. Morales、Kevin T. Mellem、Andrew G. Myers

  DOI：10.1002/anie.201200370

  日期：2012.5.7

  Unrestricted: Pseudoephenamine is introduced as a versatile chiral auxiliary and an alternative to pseudoephedrine in asymmetric synthesis. It is free from regulatory restrictions and leads to remarkable stereocontrol in alkylation reactions, especially in those that form quaternary carbon centers. Amides derived from pseudoephenamine exhibit a high propensity to be crystalline substances, and provide

  不受限制：Pseudoephenamine 被引入作为多功能手性助剂和不对称合成中伪麻黄碱的替代品。它不受监管限制，并在烷基化反应中产生显着的立体控制，特别是在那些形成季碳中心的反应中。源自伪苯胺的酰胺表现出高度倾向于成为结晶物质，并在 NMR 光谱中提供清晰、明确的信号。
• Organocatalytic Enantioselective Acyloin Rearrangement of α-Hydroxy Acetals to α-Alkoxy Ketones
  作者：Hua Wu、Qian Wang、Jieping Zhu

  DOI：10.1002/anie.201701098

  日期：2017.5.15

  We report an unprecedented organocatalytic enantioselective acyloin rearrangement of α,α‐disubstituted α‐hydroxy acetals. In the presence of a catalytic amount of chiral binol‐derived N‐triflyl phosphoramide, α‐hydroxy acetals rearranged to α‐alkoxy ketones in good to high yields with high enantioselectivities. Formation of an ion pair between the in situ generated oxocarbenium ion and the chiral phosphoramide

  我们报告了史无前例的α，α-二取代的α-羟基缩醛的有机催化对映选择性酰基肌醇重排。在催化量的手性二元醇衍生的氮存在下-三氟磷酰胺，α-羟基缩醛重排成α-烷氧基酮，具有高至高收率和高对映选择性。有人建议在原位生成的氧碳鎓离子和手性磷酰胺阴离子之间形成离子对，这是手性高效转移的原因。发现了从相应的α-烷氧基酮中除去环己基和环戊基的条件，这证明了它们作为羟基保护基团的潜在通用性。还记录了重排产物转化为对映体富集的α-羟基酮，1,2-二醇，β-氨基醇和1,4-二恶烷的过程。
• Collective Synthesis of Cladiellins Based on the Gold-Catalyzed Cascade Reaction of 1,7-Diynes
  作者：Guozong Yue、Yun Zhang、Lichao Fang、Chuang-chuang Li、Tuoping Luo、Zhen Yang

  DOI：10.1002/anie.201309449

  日期：2014.2.10

  The cladiellin family of natural products, which includes molecules with various biological activities, continues to invite new synthetic studies. A gold‐catalyzed tandem reaction of 1,7‐diynes to construct the 6‐5‐bicyclic ring systems that are present in a number of natural products was developed. This reaction was applied as the key step to realize the formal and total syntheses of nine members

  天然产物的cladiellin家族，包括具有各种生物活性的分子，继续吸引着新的合成研究。开发了金催化的1,7-二炔串联反应，以构建许多天然产物中存在的6-5双环系统。该反应被用作关键步骤，以对映和非对映选择性的方式实现了克拉迪林家族9个成员的形式化和全面合成。这种模块化且有效的方法也可用于构建其他cladiellins及其类似物，用于后续研究。
• A Concise and Versatile Double-Cyclization Strategy for the Highly Stereoselective Synthesis and Arylative Dimerization of Aspidosperma Alkaloids
  作者：Jonathan William Medley、Mohammad Movassaghi

  DOI：10.1002/anie.201200387

  日期：2012.5.7

  Building cycles: A strategy for the concise, stereoselective synthesis of aspidosperma alkaloids and related structures via a common putative diiminium ion intermediate is reported. The approach enables the dimerization of aspidosperma‐type structures at the sterically hindered C2 position. The intermediate is prepared in one step from the shown lactam through an electrophilic double‐cyclization cascade

  构建循环：报告了一种通过常见的假定二亚胺离子中间体来简明、立体选择性地合成蜘蛛精生物碱和相关结构的策略。该方法能够在空间位阻 C2 位置实现无精子型结构的二聚化。中间体是从所示的内酰胺通过亲电双环化级联一步制备的（参见方案；Tf=三氟甲磺酰基）。