N-allyl-N-(2-bromopropionyl)-p-toluenesulfonamide | 167029-87-0

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: N-allyl-N-(2-bromopropionyl)-p-toluenesulfonamide
• 英文别名: N-Allyl-N-(4-tolylsulfonyl)-2-bromopropionamide；N-allyl-N-(2-bromo-propionyl)-4-methyl-benzenesulfonamide；2-bromo-N-(4-methylphenyl)sulfonyl-N-prop-2-enylpropanamide
• CAS: 167029-87-0
• 化学式: C₁₃H₁₆BrNO₃S
• 分子量: 346.245
• InChiKey: SVRLTPPKERPSAD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  19
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.31
• 拓扑面积：
  62.8
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  N-allyl-N-(2-bromopropionyl)-p-toluenesulfonamide 在 Cu(bipy)2Br 、 氨 、 lithium 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 乙腈 为溶剂， 生成 (1R,5S)-1-Methyl-3-aza-bicyclo[3.1.0]hexan-2-one
  参考文献：
  名称：

  Conformationally constrained amino acids: a convenient approach to cis-2,3-methano-GABAs

  摘要：

  3-Aza-2-oxo-bicyclo[3.1.0]hexanes, which are opened to 2,3-methano-gamma-aminobutyric acids, are obtained in very high yields by a two step procedure from N-protected-N-allyl-alpha-Br-amides. (C) 1999 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(99)00371-8
• 作为产物：
  描述：

  N-烯丙基对甲苯磺酰胺 、 2-溴丙酰溴 在 sodium hydride 作用下， 以 苯 为溶剂， 反应 9.0h， 以80%的产率得到N-allyl-N-(2-bromopropionyl)-p-toluenesulfonamide
  参考文献：
  名称：

  Indirect Electroreductive Cyclization of N-Allyl and N-Propargylamides Using a Nickel(II) Complex as an Electron-Transfer Catalyst: Selective Formation of Halogenated and Non-halogenated Pyrrolidinones.

  摘要：

  镍(II)复合物催化的间接电还原反应在二甲基甲酰胺中进行，使用2个等量的氢原子供体二苯基膦，N-烯丙基和N-丙炔基α-溴酰胺得到了相应的吡咯烷酮，作为唯一的环化产物，产率良好；而在乙腈中，N-烯丙基α-碘酰胺的反应则得到了碘化吡咯烷酮。在这两种条件下，转型C-3 : C-4的吡咯烷酮主要生成。

  DOI：

  10.1248/cpb.43.32

文献信息

• Indirect Electroreductive Cyclization of N-Allyl and N-Propargylamides Using a Nickel(II) Complex as an Electron-Transfer Catalyst: Selective Formation of Halogenated and Non-halogenated Pyrrolidinones.
  作者：Shigeko OZAKI、Hidenori MATSUSHITA、Miho EMOTO、Hidenobu OHMORI

  DOI：10.1248/cpb.43.32

  日期：——

  Nickel(II) complex-catalyzed indirect electroreduction of N-allyl and N-propargyl-α-bromoamides conducted in dimethylformamide with 2 eq of a hydrogen atom donor, diphenylphosphine, afforded the corresponding pyrrolidinones as the sole cyclized product in good yields, while that of N-allyl-α-iodoamides in acetonitrile gave the iodinated pyrrolidinones. Under both conditions the trans-C-3 : C-4 pyrrolidinones were formed predominantly.

  镍(II)复合物催化的间接电还原反应在二甲基甲酰胺中进行，使用2个等量的氢原子供体二苯基膦，N-烯丙基和N-丙炔基α-溴酰胺得到了相应的吡咯烷酮，作为唯一的环化产物，产率良好；而在乙腈中，N-烯丙基α-碘酰胺的反应则得到了碘化吡咯烷酮。在这两种条件下，转型C-3 : C-4的吡咯烷酮主要生成。
• Atom transfer radical cyclisations of activated and unactivated N-allylhaloacetamides and N-homoallylhaloacetamides using chiral and non-chiral copper complexes
  作者：Andrew J. Clark、Floryan De Campo、Robert J. Deeth、Robert P. Filik、Sylvain Gatard、Nicola A. Hunt、Dominique Lastécouères、Gerard H. Thomas、Jean-Baptiste Verlhac、Hathaichanuk Wongtap

  DOI：10.1039/a909666c

  日期：——

  Activated N-tosyl-2,2,2-trichloroacetamide 6a, N-benzyl-2,2,2-trichloroacetamide 6d, 2,2-dichloroacetamides 6b–c and 6e–f and 2-monohaloacetamides 11a–g undergo efficient 5-exo atom transfer radical cyclisations at room temperature mediated by CuCl or CuBr in the presence of tris(N,N-dimethylaminoethylene)amine 3 (trien-Me6). The efficiency and stereoselectivity of these cyclisations was found to be greater than existing published atom transfer procedures based upon CuCl(bipyridine), RuCl2(PPh3)3 and CuCl(TMEDA)2. The product distribution for the cyclisation onto alkyne 11g was found to be solvent dependent. Attempts to make larger ring sizes by endo cyclisation of N-tosylacetamides 19a–c led to a competing 5-exoipso aromatic substitution into the N-tosyl group followed by re-aromatisation and loss of SO2 to furnish an amidyl radical. Cyclisation of N-homoallylacetamides 25a–d proceeded smoothly to give δ-lactams with a range of catalysts based upon ligands 2 and 26. The stereoselectivity of cyclisation to give γ lactams could be somewhat influenced by using chiral enantiopure copper complexes 28–30 suggesting that the reactions may involve metal-complexed radicals.

  活化的N-托烯基-2,2,2-三氯乙酰酰胺6a、N-苄基-2,2,2-三氯乙酰酰胺6d、2,2-二氯乙酰酰胺6b–c和6e–f以及2-单卤乙酰酰胺11a–g在室温下通过CuCl或CuBr以及三（N,N-二甲氨基乙烯）胺3（trien-Me6）的介导，经历了高效的5-exo原子转移自由基环化反应。这些环化反应的效率和立体选择性比现有的基于CuCl（联吡啶）、RuCl2（PPh3）3和CuCl（TMEDA）2的原子转移程序更高。环化反应在炔烃11g上的产物分布发现依赖于溶剂。尝试通过N-托烯基乙酰酰胺19a–c的内环化生成更大环的过程，导致N-托烯基基团发生竞争性的5-exo环置换，随后发生再芳香化并失去SO2，生成酰基自由基。N-同烯丙基乙酰酰胺25a–d的环化顺利进行，得到了一系列基于配体2和26的催化剂的δ-内酯。通过使用手性恩路全纯铜复合物28–30，γ-内酯的环化立体选择性受到一定影响，表明反应可能涉及金属配位自由基。
• Asymmetric induction in the inter- and intramolecular radical carbon–carbon bond forming reactions of N-arylsulfonyl-α-bromocarboxamides with chiral ligands: the use of chiral sulfoxide ligands in radical chemistry
  作者：Kunio Hiroi、Mikiyo Ishii

  DOI：10.1016/s0040-4039(00)01213-2

  日期：2000.9

  Inter- and intramolecular asymmetric radical carbon–carbon bond-forming reactions of sulfonamides were successfully achieved using chiral ligands in the presence of Lewis acids. The use of chiral sulfoxides as chiral ligands in the radical reactions of sulfonamides provided higher enantioselectivity, proceeding through a diastereomerically more favorable intermediate, presumably by enantiotopically

  在路易斯酸存在下，使用手性配体成功实现了磺酰胺类分子间和分子内不对称自由基碳-碳键形成反应。在磺酰胺的自由基反应中使用手性亚砜作为手性配体提供了更高的对映选择性，这是通过非对映异构的更有利的中间体进行的，大概是通过磺酰胺的两个氧原子之一的对位选择性配位进行的。
• Solid-Supported Catalysts for Atom-Transfer Radical Cyclization of 2-Haloacetamides
  作者：Andrew J. Clark、Robert P. Filik、David M. Haddleton、Arnaud Radigue、Christopher J. Sanders、Gerard H. Thomas、Mark E. Smith

  DOI：10.1021/jo9908896

  日期：1999.11.1
• Copper mediated atom transfer radical cyclisations with AIBN
  作者：Andrew J. Clark、Paul Wilson

  DOI：10.1016/j.tetlet.2008.06.016

  日期：2008.8

  We have shown that it is possible to mediate a range of 5-exo trig and 5-exo dig atom transfer radical cyclisations of bromoacetamides using 0.1-1 mol % CuBr or CuBT2 in conjunction with 0.1-1 mol % tri(pyridin-2-ylmethyl)amine and 10 mol % AIBN. This equates to a 30-300-fold reduction in the amount of catalyst previously reported for these reactions and allows cyclisation to be carried out with the more oxidatively stable CuBr2 without the requirement of an inert atmosphere. (C) 2008 Elsevier Ltd. All rights reserved.