trans-1-(tert-butyl)-3-(diethoxyphosphoryl)-4-phenyl-γ-lactam

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯烷类
• 英文名称: trans-1-(tert-butyl)-3-(diethoxyphosphoryl)-4-phenyl-γ-lactam
• 英文别名: (3R,4S)-1-tert-butyl-3-diethoxyphosphoryl-4-phenylpyrrolidin-2-one
• 化学式: C₁₈H₂₈NO₄P
• 分子量: 353.398
• InChiKey: RPVWQTRCZDTYIV-HZPDHXFCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  24
• 可旋转键数：
  7
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.61
• 拓扑面积：
  55.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  α-bromoacetyl-N-(tert-butyl)-N-(phenylethyl)amide 在 dirhodium tetraacetate 对甲苯磺酰叠氮 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 四氢呋喃 、 1,2-二氯乙烷 为溶剂， 反应 32.0h， 生成 trans-1-(tert-butyl)-3-(diethoxyphosphoryl)-4-phenyl-γ-lactam
  参考文献：
  名称：

  α-重氮-α-(二烷氧基磷酰基)乙酰胺和-乙酸盐的区域选择性和立体选择性二铑(II)-催化的分子内C-H插入反应

  摘要：

  α-重氮-α-（二烷氧基磷酰基）乙酸酯和 -乙酰胺分别通过二铑（II）催化的分子内碳氢插入反应以中等至高产率提供了 α-（二烷氧基磷酰基）内酯和内酰胺。在α-重氮-α-（二烷氧基磷酰基）乙酰胺的情况下，观察到显着偏好形成γ-内酰胺，立体控制有利于反式非对映异构体。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)

  DOI：

  10.1002/ejoc.200300330

文献信息

• [EN] IONIC LIQUID SOLVENTS<br/>[FR] SOLVANTS LIQUIDES IONIQUES
  申请人：UNIV DUBLIN CITY

  公开号：WO2010097412A1

  公开（公告）日：2010-09-02

  A chiral ionic compound comprising an alkyl substituted imidazolium or pyridinium cationic core having an alkyl ester side chain (-alkyl-C(O)O-) directly linked to the core and an associated counter anion, characterized in that the -O- atom of the ester side chain is linked to an alpha, a beta or a gamma hydroxycarboxylic acid functionality via the alpha, beta or gamma hydroxy of the acid functionality and the hydroxycarboxylic acid functionality has at least one asymmetric carbon, or characterized in that an -N= atom of the alkyl substituted imidazolium or pyridinium cationic core is substituted with an alpha, a beta or a gamma hydroxy group of a alpha, a beta or a gamma hydroxycarboxylic acid functionality and the hydroxycarboxylic acid functionality has at least one asymmetric carbon. The chiral ionic liquids (CILs) may be used as novel solvents, in particular for organic synthesis. The CILs have the potential to induce asymmetry into substrates or catalysts in a variety of organic transformations. A number of the compounds have low antimicrobial and low antifungal toxicities and are also biodegradable CILs.

  一种手性离子化合物，包括具有烷基取代的咪唑或吡啶阳离子核心，其具有直接连接到核心的烷基酯侧链（-烷基-C（O）O-）和相关的对应阴离子，其特征在于酯侧链的-O-原子通过α、β或γ羟基羧酸功能与羧酸功能的α、β或γ羟基相连，且羟基羧酸功能具有至少一个不对称碳，或者其特征在于烷基取代的咪唑或吡啶阳离子核心的-N=原子被α、β或γ羟基羧酸功能的α、β或γ羟基取代，且羟基羧酸功能具有至少一个不对称碳。这种手性离子液体（CILs）可用作新型溶剂，特别适用于有机合成。这些CILs有潜力在各种有机转化中向底物或催化剂引入不对称性。其中一些化合物具有低抗菌和低抗真菌毒性，并且也是可生物降解的CILs。
• Asymmetric Intramolecular CH Insertion of α-Diazoacetamides in Water by Dirhodium(II) Catalysts Derived from Natural Amino Acids
  作者：Nuno R. Candeias、Carolina Carias、Luis F. R. Gomes、Vânia André、M. Teresa Duarte、Pedro M. P. Gois、Carlos A. M. Afonso

  DOI：10.1002/adsc.201200101

  日期：2012.11.12

  The asymmetric dirhodium(II)-catalyzed intramolecular CH insertion of α-diazo acetamides in water is described for the first time. The use of natural α-amino acids as chiral ligands allowed the preparation of novel dirhodium(II) homochiral complexes by a simple procedure consisting of the in situ ligand exchange starting from dirhodium tetraacetate. The catalytic system was further reused up to 7 cycles

  首次描述了α-重氮乙酰胺在水中不对称由二碘鎓（II）催化的分子内CH插入。天然α-氨基酸作为手性配体的使用允许通过简单的程序制备新的dirhodium（II）同手性络合物，该程序包括从四乙酸dirhodium开始的原位配体交换。催化体系进一步重复使用多达7个循环，并以良好的收率和过量的对映异构体获得了β-内酰胺。
• Cyclization of Diazoacetamides Catalyzed by N-Heterocyclic Carbene Dirhodium(II) Complexes
  作者：Carlos Afonso、Luis Gomes、Alexandre Trindade、Nuno Candeias、Luís Veiros、Pedro Gois

  DOI：10.1055/s-0029-1217005

  日期：2009.10

  The axial coordination of N-heterocyclic carbene ligands onto dirhodium(II) complexes was examined, together with its role in the intramolecular C-H insertion reactions of α-diazoacetamides. The formation of a decarbonylated product occurs by a free-carbene mechanism in which the structures of the catalyst and the acetamide play a decisive role. carbenoids - carbene complexes - catalysis - diazo compounds

  研究了N-杂环卡宾配体在dirhodium（II）配合物上的轴向配位，及其在α-重氮乙酰胺的分子内CH插入反应中的作用。脱羰基产物的形成是通过游离碳烯机理进行的，其中催化剂和乙酰胺的结构起决定性作用。 类胡萝卜素-卡宾配合物-催化-重氮化合物-铑
• Ionic liquid solvents
  申请人：Dublin City University

  公开号：EP2223915A1

  公开（公告）日：2010-09-01

  A chiral ionic compound comprising an alkyl substituted imidazolium cationic core having an alkyl ester side chain (-alkyl-C(O)O-) directly linked to the core and an associated counter anion, characterized in that the -O- atom of the ester side chain is linked to an alpha, a beta or a gamma hydroxycarboxylic acid functionality via the alpha, beta or gamma hydroxy of the acid functionality and the hydroxycarboxylic acid functionality has at least one asymmetric carbon.The chiral ionic liquids (CILs)may be used as novel solvents for organic synthesis. The CILs have the potential to induce asymmetry into substrates or catalysts in a variety of organic transformations. A number of the compounds are biodegradable CILs.

  一种手性离子化合物，包括一个烷基取代的咪唑阳离子核心，该核心具有一个直接连接到核心的烷基酯侧链（-烷基-C(O)O-）和一个相关的反离子、 手性离子液体（CIL）可用作有机合成的新型溶剂。手性离子液体（CILs）可用作有机合成的新型溶剂。CILs 具有在各种有机转化过程中诱导底物或催化剂产生不对称的潜力。其中一些化合物是可生物降解的 CIL。
• C−H Carbene Insertion of α-Diazo Acetamides by Photolysis in Non-Conventional Media
  作者：Nuno R. Candeias、Pedro M. P. Gois、Luis F. Veiros、Carlos A. M. Afonso

  DOI：10.1021/jo800980c

  日期：2008.8.1

  Light from a mercury vapor high-pressure lamp was used to induce the photolytic decomposition of alpha-diazo acetamides in hexane and in nonconventional media such as water or a film. The corresponding beta- and/or gamma-lactams were obtained in reasonable yields and in some cases with good diastereoselectivities with no need to use a metallic catalyst. Experimental studies on chiral substrates demonstrated the occurrence of insertion with retention of configuration.