N-tosyl-α,α-dichloro-α-methyl-allylacetamide | 154330-95-7

• 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-tosyl-α,α-dichloro-α-methyl-allylacetamide
• 英文别名: N-allyl-N-(2,2-dichloropropionyl)-4-methylbenzenesulfonamide；N-Allyl-N-(4-tolylsulfonyl)-2,2-dichloro-2-methylacetamide；N-allyl-N-4-toluenesulfonyl-2,2-dichloro-2-methylacetamide；N-allyl-N-4-toluenesulfonyl-2,2-dichloropropionamide；2,2-dichloro-N-(4-methylphenyl)sulfonyl-N-prop-2-enylpropanamide
• CAS: 154330-95-7
• 化学式: C₁₃H₁₅Cl₂NO₃S
• 分子量: 336.239
• InChiKey: DNGCQIQYCKRFPD-UHFFFAOYSA-N

物化性质

• 沸点：
  415.8±55.0 °C(Predicted)
• 密度：
  1.332±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  20
• 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-tosyl-α,α-dichloro-α-methyl-allylacetamide 在 tris(triphenylphosphine)ruthenium(II) chloride 作用下， 以 苯 为溶剂， 反应 4.0h， 生成 3-chloro-4-chloromethyl-1-(p-toluenesulfonyl)-pyrrolidin-2-one 、 (3RS,4SR)-4-chloromethyl-3-chloro-3-methyl-1-toluene-4-sulfonylpyrrolidin-2-one
  参考文献：
  名称：

  Ruthenium (II) catalyzed ring closure of prochiral α-chloro-N-tosyl amides: A diastereoselectivity study.

  摘要：

  Prochiral N-tosyl amides cyclized under (Ph3P)3RuCl2 catalysis gave diastereomeric 2-pyrrolidinone products. Stereoselectivity depended upon the size of C2-substitutents

  DOI：

  10.1016/s0040-4039(00)91804-5
• 作为产物：
  描述：

  2,2-二氯丙酰氯 、 N-烯丙基对甲苯磺酰胺 在 sodium hydride 作用下， 生成 N-tosyl-α,α-dichloro-α-methyl-allylacetamide
  参考文献：
  名称：

  Ruthenium (II) catalyzed ring closure of prochiral α-chloro-N-tosyl amides: A diastereoselectivity study.

  摘要：

  Prochiral N-tosyl amides cyclized under (Ph3P)3RuCl2 catalysis gave diastereomeric 2-pyrrolidinone products. Stereoselectivity depended upon the size of C2-substitutents

  DOI：

  10.1016/s0040-4039(00)91804-5

文献信息

• 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。
• Electrochemical Approach to Copper-Catalyzed Reversed Atom Transfer Radical Cyclization
  作者：Abdirisak A. Isse、Giulia Visonà、Franco Ghelfi、Fabrizio Roncaglia、Armando Gennaro

  DOI：10.1002/adsc.201400587

  日期：2015.3.9

  atom transfer radical cyclization (eATRC) has been developed as an easy and clean method allowing the synthesis of halogenated cyclic compounds. This method has been successfully applied to the copper‐catalyzed atom transfer radical cyclization of some N‐allyl‐α,α‐dichloroamides in acetonitrile (CH3CN) using a copper complex with tris(2‐pyridylmethyl)amine (TPMA) with a metal loading of 1%. The catalyst

  电化学介导的原子转移自由基环化（e ATRC）已被开发为一种易于清洁的方法，可合成卤代环状化合物。该方法已成功地用于铜与三（2-吡啶基甲基）胺（TPMA）的铜配合物在乙腈（CH 3 CN）中的某些N-烯丙基-α，α-二氯酰胺的铜催化原子转移自由基环化反应中金属含量为1％。催化剂以[Cu（II）TPMA] 2+的形式引入，并通过在铂（Pt）电极上还原而被活化并连续再生为活性铜（I）形式。在ATRC过程中，新的铜（II）络合物[ClCu（II）TPMA] +的还原电势约为。形成比起始[Cu（II）TPMA] 2+负的电压多0.350V 。因此，选择施加的电势至关重要，并且应注意将所有铜（II）物种还原为铜（I）。这些化合物在电解数小时后会经历很高的转化率（79–100％），以两种异构体的混合物形式生成环状γ-内酰胺（收率60–98％），并具有良好的顺-非对映选择性[ dr（cis / trans）=
• 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.
• N-alkyl-2-pyridylmethanimines as tuneable alternatives to bipyridine ligands in copper mediated atom transfer radical cyclisation
  作者：Andrew J. Clark、David J. Duncalf、Robert P. Filik、David M. Haddleton、Gerard H. Thomas、Hathaichanuk Wongtap

  DOI：10.1016/s0040-4039(99)00533-x

  日期：1999.5

  Copper halide complexes of N-alkyl-2-pyridylmethanimines (3, 11-14) catalyse atom transfer radical cyclisation reactions of activated (6a-b) and unactivated alpha-haloallylacetamides (9) at room temperature. (C) 1999 Elsevier Science Ltd. All rights reserved.
• 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.