(E)-4-(4-bromophenyl)-1,1,1-trichlorobut-3-en-2-one | 1201890-10-9

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 肉桂酸及其衍生物
• 英文名称: (E)-4-(4-bromophenyl)-1,1,1-trichlorobut-3-en-2-one
• CAS: 1201890-10-9
• 化学式: C₁₀H₆BrCl₃O
• 分子量: 328.42
• InChiKey: APYFMRZOQSJQOP-ZZXKWVIFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.6
• 重原子数：
  15
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.1
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  1-oxo-3-phenylpropan-2-yl 4-nitrobenzoate 、 (E)-4-(4-bromophenyl)-1,1,1-trichlorobut-3-en-2-one 在 (5aR,10bS)-5a,10b-dihydro-2-(2,4,6-trimethylphenyl)-4H,6H-indeno[2,1-b]-1,2,4-triazolo[4,3-d]-1,4-oxazinium chloride 、 三乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 1.5h， 以55%的产率得到(3S,4S)-3-benzyl-4-(4-bromophenyl)-6-(trichloromethyl)-3,4-dihydro-2H-pyran-2-one
  参考文献：
  名称：

  Enantioselective NHC-Catalyzed Redox [4 + 2]-Hetero-Diels–Alder Reactions Using α,β-Unsaturated Trichloromethyl Ketones as Amide Equivalents

  摘要：

  alpha,beta-Unsaturated trichloromethyl ketones are suitable a alpha,beta-unsaturated amide and ester equivalents in N-heterocyclic carbene (NHC)-catalyzed redox hetero-Diels Alder reactions with azolium enolates generated from alpha-aroyloxyaldehydes. The initially formed syn-dihydropyranone products can be isolated or can undergo ring-opening with benzylamine followed by aminolysis of the resulting CCl3 ketone to form a range of diamides with high diastereo- and enantioselectivity (up to >95:5 dr and >99% ee).

  DOI：

  10.1021/acs.joc.5b01820
• 作为产物：
  描述：

  3-(4-溴苯基)丙-2-烯-1-醇 在 manganese(IV) oxide 、 三氧化硫吡啶 、 三乙胺 、 potassium hydroxide 作用下， 以 二氯甲烷 、 二甲基亚砜 、 N,N-二甲基甲酰胺 为溶剂， 反应 53.5h， 生成 (E)-4-(4-bromophenyl)-1,1,1-trichlorobut-3-en-2-one
  参考文献：
  名称：

  Enantioselective NHC-Catalyzed Redox [4 + 2]-Hetero-Diels–Alder Reactions Using α,β-Unsaturated Trichloromethyl Ketones as Amide Equivalents

  摘要：

  alpha,beta-Unsaturated trichloromethyl ketones are suitable a alpha,beta-unsaturated amide and ester equivalents in N-heterocyclic carbene (NHC)-catalyzed redox hetero-Diels Alder reactions with azolium enolates generated from alpha-aroyloxyaldehydes. The initially formed syn-dihydropyranone products can be isolated or can undergo ring-opening with benzylamine followed by aminolysis of the resulting CCl3 ketone to form a range of diamides with high diastereo- and enantioselectivity (up to >95:5 dr and >99% ee).

  DOI：

  10.1021/acs.joc.5b01820

文献信息

• Isothiourea-Catalyzed Enantioselective Functionalization of 2-Pyrrolyl Acetic Acid: Two-Step Synthesis of Stereodefined Dihydroindolizinones
  作者：Shuyue Zhang、James E. Taylor、Alexandra M. Z. Slawin、Andrew D. Smith

  DOI：10.1021/acs.orglett.8b02423

  日期：2018.9.7

  Catalytic enantioselective functionalization of 2-pyrrolyl acetic acid with trichloromethyl enones using isothiourea catalysis is reported, leading to a range of stereodefined diesters and diamides after nucleophilic ring opening with either methanol or benzylamine (30 examples, up to >95:5 dr and >99:1 er). Subsequent intramolecular Friedel–Crafts reaction allows access to dihydroindolizinones in high yields

  据报道，使用异硫脲催化三氯甲基烯酮对2-吡咯基乙酸的催化对映选择性官能化，导致在用甲醇或苄基胺亲核开环后产生一系列立体定义的二酯和二酰胺（30个实例，高达> 95：5 dr和> 99 ：1 er）。随后的分子内Friedel-Crafts反应可实现高收率和立体保真度的二氢吲哚并酮（6个实例，高达> 95：5 dr和99：1 er）。
• Highly Efficient Asymmetric Epoxidation of Electron-Deficient α,β-Enones and Related Applications to Organic Synthesis
  作者：Changwu Zheng、Yawen Li、Yingquan Yang、Haifeng Wang、Haifeng Cui、Junkang Zhang、Gang Zhao

  DOI：10.1002/adsc.200900041

  日期：2009.7

  The asymmetric epoxidation of electron‐deficient olefins has been achieved using inexpensive and readily available prolinols as catalysts with good to excellent yields and enantioselectivities. The utility of the resulting chiral epoxides was illustrated by elaboration to several synthetically useful compounds featuring a concise synthesis of (−)‐(5R,6S)‐balasubramide.

  使用价格低廉，易于获得的脯氨醇作为催化剂，可以实现电子不足的烯烃的不对称环氧化，其收率和对映选择性都非常好。详细阐述了几种合成有用的化合物，这些化合物以（-）-（5 R，6 S）-巴拉苏酰胺的简明合成为例，说明了所得手性环氧化物的实用性。
• Enantioselective NHC-Catalyzed Redox [4 + 2]-Hetero-Diels–Alder Reactions Using α,β-Unsaturated Trichloromethyl Ketones as Amide Equivalents
  作者：Nassilia Attaba、James E. Taylor、Alexandra M. Z. Slawin、Andrew D. Smith

  DOI：10.1021/acs.joc.5b01820

  日期：2015.10.2

  alpha,beta-Unsaturated trichloromethyl ketones are suitable a alpha,beta-unsaturated amide and ester equivalents in N-heterocyclic carbene (NHC)-catalyzed redox hetero-Diels Alder reactions with azolium enolates generated from alpha-aroyloxyaldehydes. The initially formed syn-dihydropyranone products can be isolated or can undergo ring-opening with benzylamine followed by aminolysis of the resulting CCl3 ketone to form a range of diamides with high diastereo- and enantioselectivity (up to >95:5 dr and >99% ee).