N-Benzyl-2,2,2-trichloro-N-(1-methyl-allyl)-acetamide | 122722-30-9

• 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-Benzyl-2,2,2-trichloro-N-(1-methyl-allyl)-acetamide
• 英文别名: N-benzyl-N-but-3-en-2-yl-2,2,2-trichloroacetamide
• CAS: 122722-30-9
• 化学式: C₁₃H₁₄Cl₃NO
• 分子量: 306.619
• InChiKey: SWVDMECHAICQHY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.1
• 重原子数：
  18
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.31
• 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-Benzyl-2,2,2-trichloro-N-(1-methyl-allyl)-acetamide 以93%的产率得到
  参考文献：
  名称：

  NAGASHIMA, HIDEO;OZAKI, NOBUYASU;SEKI, KOJI;ISHII, MASAYUKI;ITOH, KENJI, J. ORG. CHEM., 54,(1989) N9, C. 4497-4499

  摘要：

  DOI：
• 作为产物：
  描述：

  N-benzyl(but-3-en-2-yl)amine 在 三乙胺 作用下， 以 乙醚 为溶剂， 生成 N-Benzyl-2,2,2-trichloro-N-(1-methyl-allyl)-acetamide
  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

• 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。
• DPPF-Catalyzed Atom-Transfer Radical Cyclization via Allylic Radical
  作者：Longlei Hou、Zhaozhao Zhou、Dong Wang、Yuwen Zhang、Xin Chen、Lijin Zhou、Yang Hong、Wei Liu、Yading Hou、Xiaofeng Tong

  DOI：10.1021/acs.orglett.7b03135

  日期：2017.12.1

  A general iron-catalyzed strategy for the atom-transfer radical cyclization (ATRC) of allylic halide is reported. Critical to this strategy is the use of DPPF [1,1′-bis(diphenylphosphino)ferrocene] as catalyst, which allows for efficient generation of the allylic radical species via a single-electron transfer (SET) process. The feasibility of achieving ATRC reactions of propargyl chlorides is also

  报道了烯丙基卤化物的原子转移自由基环化（ATRC）的一般铁催化策略。该策略的关键是使用DPPF [1,1'-双（二苯基膦基）二茂铁]作为催化剂，该催化剂可通过单电子转移（SET）工艺有效生成烯丙基自由基。还证明了实现炔丙基氯的ATRC反应的可行性，其提供了具有环外烯丙基部分的产物。
• The influence of benzylic protection and allylic substituents on the CuCl-TMEDA catalyzed rearrangement of N-allyl-N-benzyl-2,2-dihaloamides to γ-lactams. Application to the stereoselective synthesis of pilolactam
  作者：Franco Ghelfi、Franco Bellesia、Luca Forti、Gianluca Ghirardini、Romano Grandi、Emanuela Libertini、Maria C Montemaggi、Ugo M Pagnoni、Adriano Pinetti、Laurent De Buyck、Andrew F Parsons

  DOI：10.1016/s0040-4020(99)00247-1

  日期：1999.4

  A number of N-benzylic protecting groups and allylic substituents have been investigated for the rearrangement, promoted by CuCl-TMEDA, of N-allyl-2,2-dihaloamides to 3,4-disubstituted gamma-lactams. An appreciable chiral induction was observed at the C-4 site when alpha-phenylethylamine was used as a chiral protecting group, while an unexpected Diels-Alder reaction occurred when using a 2-furyl-methyl protection. This rearrangement has been applied to the synthesis of pilolactam, a drug with muscarinic activity. (C) 1999 Elsevier Science Ltd. All rights reserved.
• NAGASHIMA, HIDEO;OZAKI, NOBUYASU;SEKI, KOJI;ISHII, MASAYUKI;ITOH, KENJI, J. ORG. CHEM., 54,(1989) N9, C. 4497-4499
  作者：NAGASHIMA, HIDEO、OZAKI, NOBUYASU、SEKI, KOJI、ISHII, MASAYUKI、ITOH, KENJI

  DOI：——

  日期：——
• Highly stereoselective radical cyclization: copper or ruthenium-catalyzed preparation of cis- and trans-.beta.,.gamma.-dialkyl .gamma.-lactams from acyclic N-allyltrichloroacetamide derivatives
  作者：Hideo Nagashima、Nobuyasu Ozaki、Koji Seki、Masayuki Ishii、Kenji Itoh

  DOI：10.1021/jo00280a011

  日期：1989.9