N-allyl-N-benzyl-2,2,2-trichloroacetamide | 91989-79-6

• 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-benzyl-2,2,2-trichloroacetamide
• 英文别名: N-allyl-N-benzyl-trichloroacetamide；N-benzyl-2,2,2-trichloro-N-prop-2-enylacetamide
• CAS: 91989-79-6
• 化学式: C₁₂H₁₂Cl₃NO
• 分子量: 292.592
• InChiKey: MVCXZKRFDRQYQQ-UHFFFAOYSA-N

物化性质

• 熔点：
  43.9-44.6 °C
• 沸点：
  346.6±42.0 °C(Predicted)
• 密度：
  1.318±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  17
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  20.3
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  N-allyl-N-benzyl-2,2,2-trichloroacetamide 在 Noyori's catalyst 、 异丙基氯化镁 、 戴斯-马丁氧化剂 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 4.67h， 生成 (R)-N-allyl-N-benzyl-2,2-dichloro-3-hydroxybutanamide
  参考文献：
  名称：

  钌催化不对称转移加氢合成对映体富集的α，α-二氯-和α，α-二氟-β-羟基酯和酰胺

  摘要：

  通过使用市售的Noyori配合物[RuCl（p- Cymene）（R，R）-TsDPEN]作为催化剂（S / C = 100-200）在相应的酮的不对称转移氢化中。对于一系列不同取代的二氯和二氟β-羟基酯和酰胺，可实现中等至高收率（高达99％）和出色的对映选择性（高达> 99％ee）。

  DOI：

  10.1021/acs.orglett.8b01943
• 作为产物：
  描述：

  N-烯丙基苄胺 在 三乙胺 作用下， 以 乙醚 为溶剂， 生成 N-allyl-N-benzyl-2,2,2-trichloroacetamide
  参考文献：
  名称：

  Transition metal-catalyzed radical cyclizations: a low-temperature process for the cyclization of N-protected N-allyltrichloroacetamides to trichlorinated .gamma.-lactams and application to the stereoselective preparation of .beta.,.gamma.-disubstituted .gamma.-lactams

  摘要：

  Cyclizations of N-substituted N-allyltrichloroacetamides, where the substituent is an alkyl, Cbz, Boc, Ts, or Ms group, are catalyzed by a 1:1 mixture of CuCl and bipyridine to give the corresponding beta,gamma-trichlorinated gamma-lactams in high yields. The reactions proceed at temperatures from -78-degrees-C to room temperature. Cyclizations of N-allyltrichloroacetamides of acyclic secondary allylic amines are achieved with good selectivity; the cis/trans ratios of the gamma-lactams formed were dependent on the substituents on the nitrogen atom. The stereochemical outcome is compared with that of free-radical cyclization.

  DOI：

  10.1021/jo00054a034

文献信息

• Radical Reactions Using Decacarbonyldimanganese under Biphasic Conditions
  作者：Nathalie Huther、P. Terry McGrail、Andrew F. Parsons

  DOI：10.1002/ejoc.200400025

  日期：2004.4

  cyclisations and intermolecular addition reactions were performed under these conditions. This included the development of a new tandem radical addition−ionic cyclisation sequence that was employed in a short approach to (±)-coronamic acid. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)

  在十羰基二锰存在下由光解引发的烷基卤化物的自由基反应可以在双相介质中进行。在氢氧化钠水溶液和相转移催化剂存在下的反应可有效去除卤化锰副产物，并导致十羰基二锰的再生。在这些条件下进行了一系列有效的自由基偶联、环化和分子间加成反应。这包括开发了一种新的串联自由基加成 - 离子环化序列，该序列用于（±）-冠酸的短方法。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)
• Synthesis of α-Chlorolactams by Cyanoborohydride-Mediated Radical Cyclization of Trichloroacetamides
  作者：Guilhem Coussanes、Harald Jakobi、Stephen Lindell、Josep Bonjoch

  DOI：10.1002/chem.201800210

  日期：2018.6.7

  A cyanoborohydride‐promoted radical cyclization methodology has been developed to access α‐chlorolactams in a simple and efficient way using NaBH3CN and trichloroacetamides easily available from allylic and homoallylic secondary amines. This methodology allowed the synthesis of a library of α‐chlorolactams (mono‐ and bicyclic), which were tested for herbicidal activity, trans‐3‐chloro‐4‐methyl‐1‐(

  已开发出一种氰基硼氢化物促进的自由基环化方法，可使用NaBH 3 CN和三氯乙酰胺（可从烯丙基和均烯丙基仲胺中轻松获得）以简单有效的方式获得α-氯内酰胺。这种方法学允许合成α-氯内酰胺（单环和双环）文库，并对其除草活性进行了测试，反式-3-氯-4-甲基-1-（3-三氟甲基）苯基-2-吡咯烷酮是最活跃。
• Catalytic atom-transfer radical cyclization by copper/bipyridine species encapsulated in polysiloxane gel
  作者：Yukihiro Motoyama、Kazuyuki Kamo、Akihiro Yuasa、Hideo Nagashima

  DOI：10.1039/b923213c

  日期：——

  Novel polysiloxane gel, in which CuCl/bipyridine species are immobilized, is prepared by treatment of polymethylhydrosiloxane with 4,4′-bis[(2-propenyl)oxy]-2,2′-bipyridine and 1,5-hexadine in the presence of Karstedt′s catalyst followed by addition of CuCl. This polysiloxane gel acts as a reusable catalyst in the atom-transfer radical cyclization of α-halogenated acetamide derivatives in high turnover numbers without allowing leakage of the metal species.

  一种新型聚硅氧烷凝胶被制备，通过在Karstedt催化剂的存在下，用4,4′-双[(2-丙烯基)氧]-2,2′-联吡啶和1,5-己二烯处理聚甲基氢硅氧烷，然后加入CuCl。这种聚硅氧烷凝胶在α-卤代乙酰胺衍生物的原子转移自由基环化中作为可重复使用的催化剂，表现出高的循环次数且不允许金属物种泄漏。
• 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。
• Electro‐Mechanochemical Atom Transfer Radical Cyclizations using Piezoelectric BaTiO ₃
  作者：Christian Schumacher、José G. Hernández、Carsten Bolm

  DOI：10.1002/anie.202003565

  日期：2020.9.14

  formation and regeneration of active CuI species is a fundamental mechanistic step in copper‐catalyzed atom transfer radical cyclizations (ATRC). Typically, the presence of the catalytically active CuI species in the reaction mixture is secured by using high CuI catalyst loadings or the addition of complementary reducing agents. In this study it is demonstrated how the piezoelectric properties of barium

  活性Cu I物种的形成和再生是铜催化原子转移自由基环化（ATRC）的基本机理步骤。通常，通过使用高Cu I催化剂负载量或添加还原性还原剂来确保反应混合物中催化活性Cu I物质的存在。在这项研究中，证明了如何通过机械球磨法利用钛酸钡（BaTiO 3）的压电特性在应变压电材料中引起电极化。这种策略可以将机械能转化为电能，从而将Cu II预催化剂还原为活性Cu I 铜催化的机械化学无溶剂ATRC反应中的所有物种。