1-benzyl-4-cyclohex-1-enyl-3,3-dimethylazetidin-2-one

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 内酰胺类
• 英文名称: 1-benzyl-4-cyclohex-1-enyl-3,3-dimethylazetidin-2-one
• 英文别名: N-benzyl-4-cyclohex-1-enyl-3,3-dimethylazetidin-2-one；1-Benzyl-4-(cyclohexen-1-yl)-3,3-dimethylazetidin-2-one
• 化学式: C₁₈H₂₃NO
• 分子量: 269.387
• InChiKey: BPFQRCKTYAUDPT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  20
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  20.3
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  N-(cyclohexylmethylidene)benzylamine 在 JandaJel-supported TEDETA copper(I) bromide N,N-二乙基苯胺 作用下， 以 1,2-二氯乙烷 、 甲苯 为溶剂， 反应 16.0h， 生成 1-benzyl-4-cyclohex-1-enyl-3,3-dimethylazetidin-2-one
  参考文献：
  名称：

  Solid-Supported Copper Catalysts for Atom-Transfer Radical Cyclizations:  Assessment of Support Type and Ligand Structure on Catalyst Performance in the Synthesis of Nitrogen Heterocycles

  摘要：

  A range of solid supported pyridinemethanimine 9-11 and polyamine 12-15 ligands have been prepared on silica, polystyrene, and JandaJel supports. The CuCl and CuBr complexes of these supported ligands have been used to assess both the effect of the ligand type and the nature of the support upon a representative range of copper-mediated atom transfer 5-exo-trig 6, 24-25, 5-exo-dig 26, 4-exo-trig 28, and 5-endo-trig 27, 38 radical cyclizations to give nitrogen heterocycles. In addition, the effect of the nature of the support on the stereochemical outcome of the 5-exo cyclization of 25 has been probed. Generally, it was found that the type of support (e.g., polystyrene, silica, or JandaJel) had very little effect upon the efficiency and selectivity of the processes but that the nature of the ligand type immobilized was the important factor. Thus, the 5-exo cyclization of 6 and 24-26 proceeded more rapidly with the PMI ligands 9-11, whereas 4-exo cyclizations 28 and 5-endo, radical polar crossover reactions 27 and 38 proceeded more efficiently with the JJ-TEDETA ligand 15. The efficiency of the supported ligands was also compared to their solution counterparts 4 and 5. The reusability of P-PMDETA ligand system 13 was assessed in the cyclization of 6.

  DOI：

  10.1021/jo0521605

文献信息

• The synthesis of functionalised β- and γ-lactams by cyclisation of enamides using copper(I) or ruthenium(II)
  作者：Justin S Bryans、Nicola E.A Chessum、Andrew F Parsons、Franco Ghelfi

  DOI：10.1016/s0040-4039(01)00320-3

  日期：2001.4

  regioselectivity of the radical cyclisation, which can proceed via either a 4-exo or 5-endo pathway, to form β- or γ-lactam products respectively, is determined by the nature of the metal oxidant and the reaction conditions. Thus, whereas copper(I)/bipyridine reactions give predominantly γ-lactams, the use of copper(I)/TMEDA or dichlorotris(triphenylphosphine)ruthenium(II) affords mainly β-lactams.

  已经研究了各种卤代酰胺与铜（I）或钌（II）配合物的环化作用。自由基环化的区域选择性可以通过4- exo或5- endo途径进行，分别形成β-或γ-内酰胺产物，这取决于金属氧化剂的性质和反应条件。因此，尽管铜（I）/联吡啶反应主要产生γ-内酰胺，但是使用铜（I）/ TMEDA或二氯三（三苯基膦）钌（II）主要提供β-内酰胺。
• Cu⁰-Promoted Cyclisation of Unsaturated α-Halogeno Amides To Give β- and γ-Lactams
  作者：Andrew J. Clark、Jonathan N. Duckmanton、Fulvia Felluga、Armando Gennaro、Franco Ghelfi、Jack R. D. Hardiman、Abdirisak A. Isse、Claudia Manferdini、Domenico Spinelli

  DOI：10.1002/ejoc.201600249

  日期：2016.5

  Efficient 5-exo-trig atom-transfer radical cyclisation of 13 unsaturated α-halogeno amides mediated by Cu0 (copper wire) with tripyridylmethanimine ligand (TPMA; 1 mol-%) in a mixed solvent of EtOAc/EtOH (3:1) is reported (89–98 %), with recycling of the copper wire. A substantial improvement in conversion and selectivity was obtained when Na2CO3 (5 mol-%) was added to the reaction mixture. The Cu0

  在 EtOAc/EtOH (3:1) 的混合溶剂中，由 CuO（铜线）与三吡啶基甲亚胺配体（TPMA；1 mol-%）介导的 13 种不饱和 α-卤代酰胺的有效 5-exo-trig 原子转移自由基环化是报告 (89–98%)，回收铜线。当将 Na2CO3 (5 mol-%) 添加到反应混合物中时，转化率和选择性得到显着改善。CuO 在 SARA-ATRC 工艺中充当辅助活化剂和还原剂。该方案扩展到炔烃的环化和β-内酰胺的形成，尽管这些反应的产率较低（35-76%）。
• Efficient β-lactam synthesis via 4-exo atom transfer radical cyclisation using CuBr(tripyridylamine) complex
  作者：Andrew J Clark、Gary M Battle、Andrew Bridge

  DOI：10.1016/s0040-4039(01)00737-7

  日期：2001.6

  The tripyridylamine copper(I) halide complex mediates the atom transfer radical cyclisation of bromo-enamides to give β-lactams exclusively with no formation of γ-lactams. Initial products 7 arise from 4-exo bromine atom transfer but elimination can be readily achieved by reaction with DBU to furnish alkenes 8 in high yields (92–98%).

  三吡啶胺铜（I）卤化物络合物介导溴-酰胺的原子转移自由基环化，仅生成β-内酰胺，而不会形成γ-内酰胺。初始产物7来自4- exo溴原子转移，但消除反应可通过与DBU反应以高产率（92-98％）提供烯烃8来轻松实现。
• Atom-Transfer Cyclization with CuSO₄/KBH₄: A Formal “Activators Generated by Electron Transfer” Process Also Applicable to Atom-Transfer Polymerization
  作者：Andrew J. Clark、Alana E. C. Collis、David J. Fox、Lauren L. Halliwell、Natalie James、Rachel K. O’Reilly、Hemal Parekh、Andrew Ross、Andrew B. Sellars、Helen Willcock、Paul Wilson

  DOI：10.1021/jo301429a

  日期：2012.8.17

  The 4-exo and 5-exo-trig atom-transfer cyclizations of 1, 8a-e, 9, 12, and 13 can be mediated with as little as 0.05 mol % of Cu(TPMA)SO4 center dot 5H(2)O in the presence of 2.5 mol % of borohydride salts in 10 min at room temperature in air. This formal "activators generated by electron transfer" (AGET) procedure utilizes a cheap and oxidatively stable copper source (CuSO4 center dot 5H(2)O) and can be carried out in environmentally benign solvents (EtOH). It is possible to alter the product distribution in the 5-endo radical-polar crossover reactions of 10a,b and 11 by tailoring the amount of borohydride. Cyclization onto alkynes 14 and 15 is also possible in only 20 min. Controlled radical polymerization of styrene, with increased rates over conventional atom-transfer radical polymerization (ATRP), can be carried out in a controlled fashion (Mn, PDI) using either CuBr or CuSO4 center dot 5H(2)O and Bu4NBH4.
• Solid-Supported Copper Catalysts for Atom-Transfer Radical Cyclizations:  Assessment of Support Type and Ligand Structure on Catalyst Performance in the Synthesis of Nitrogen Heterocycles
  作者：Andrew J. Clark、Joanna V. Geden、Stephen Thom

  DOI：10.1021/jo0521605

  日期：2006.2.1

  A range of solid supported pyridinemethanimine 9-11 and polyamine 12-15 ligands have been prepared on silica, polystyrene, and JandaJel supports. The CuCl and CuBr complexes of these supported ligands have been used to assess both the effect of the ligand type and the nature of the support upon a representative range of copper-mediated atom transfer 5-exo-trig 6, 24-25, 5-exo-dig 26, 4-exo-trig 28, and 5-endo-trig 27, 38 radical cyclizations to give nitrogen heterocycles. In addition, the effect of the nature of the support on the stereochemical outcome of the 5-exo cyclization of 25 has been probed. Generally, it was found that the type of support (e.g., polystyrene, silica, or JandaJel) had very little effect upon the efficiency and selectivity of the processes but that the nature of the ligand type immobilized was the important factor. Thus, the 5-exo cyclization of 6 and 24-26 proceeded more rapidly with the PMI ligands 9-11, whereas 4-exo cyclizations 28 and 5-endo, radical polar crossover reactions 27 and 38 proceeded more efficiently with the JJ-TEDETA ligand 15. The efficiency of the supported ligands was also compared to their solution counterparts 4 and 5. The reusability of P-PMDETA ligand system 13 was assessed in the cyclization of 6.