1-((1R,2S)-2-Benzenesulfonyl-3-bromomethyl-1-nitromethyl-but-3-enyl)-4-methoxy-benzene | 142076-05-9

• 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: 1-((1R,2S)-2-Benzenesulfonyl-3-bromomethyl-1-nitromethyl-but-3-enyl)-4-methoxy-benzene
• 英文别名: (3SR,4SR)-2-(Bromomethyl)-4-(4-methoxyphenyl)-5-nitro-3-(phenylsulfonyl)-1-pentene
• CAS: 142076-05-9；142076-40-2
• 化学式: C₁₉H₂₀BrNO₅S
• 分子量: 454.341
• InChiKey: FQORODLRAVEWMN-RTBURBONSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.85
• 重原子数：
  27.0
• 可旋转键数：
  9.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.26
• 拓扑面积：
  86.51
• 氢给体数：
  0.0
• 氢受体数：
  5.0

反应信息

• 作为产物：
  描述：

  4-甲氧基-β-硝基苯乙烯 、 2-(bromomethyl)-3-(phenylsulfonyl)-1-propene 在 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 六甲基磷酰三胺 、 正己烷 为溶剂， 以54%的产率得到(2SR,3RS,4SR)-3-(4-Methoxyphenyl)-1-methylene-4-nitro-2-(phenylsulfonyl)cyclopentane
  参考文献：
  名称：

  Synthesis of nitrocyclopentanes via a 3+2 strategy

  摘要：

  Reactions of 1-(phenylsulfonyl)-2-methylene-3-bromopropane (1) with various nitroolefins have been investigated with the purpose of devising a tandem [3 + 2]-annulation leading to nitro-substituted derivatives of methylenecyclopentanes. The conjugate addition step occurred readily affording 4a-e (syn) and 5a-e (anti) adducts. The anti-adducts cyclized further in the presence of HMPA to give stereoisomeric methylenecyclopentane derivatives 6a-f and 7a-f. At higher reaction temperature, partial ring closure of 4a-d-syn isomers to give cis-2,3-disubstituted cyclopentanes 8a-d could also be achieved. Base-induced equilibration provided in a one-vessel operation, starting from 1 and 1-nitrobutene (3b), the methylenecyclopentane 6b with three stereogenic centers. The difference in the stereochemical outcome of the Michael addition step with nitroolefins, as compared with reactions in which alpha,beta-unsaturated esters served as acceptors for 1, may be attributed to the better chelating ability of the lithium counterion in the latter reactions, based upon the results obtained in conjugate additions of methallyl sulfone 9 with 1-nitropropene and crotonic ester. The presence of HPMA strongly influenced the stereochemical outcome of reactions of 9 with ethyl crotonate but not with 1-nitropropene as the Michael acceptor. Reactions of 1 with 1-nitro-2-arylethenes afforded trans-trans-substituted methylenecyclopentanes as the major products. The reaction of 1 with 1-nitrocyclohexene afforded the cis-hydrindane derivative 21. The described reactions provide the first example of intramolecular trapping of nitronates resulting from Michael additions by alkyl/allyl halides.

  DOI：

  10.1021/jo00076a035

文献信息

• Michael reactions of allylic sulfones with nitroolefins. Regio- and stereochemical control
  作者：Eugene Ghera、Efrat Ben-Yaakov、Tamar Yechezkel、Alfred Hassner

  DOI：10.1016/s0040-4039(00)79071-x

  日期：1992.5

  Michael addition of allylsulfone carbanions to nitroolefins where shown to be sensitive to substitution in both the donor and the acceptor. While sulfone 10 gave predominantly products of γ-addition with aromatic nitroolefins, addition to aliphatic nitroolefins produced almost exclusively α-adducts. In the presence of an OH function in the sulfone (see 13) only (Z) γ-adducts were observed, while a

  烯丙基砜碳负离子在硝基烯烃上的迈克尔加成反应对供体和受体均表现出对取代敏感的作用。砜10主要产生与芳族硝基烯烃的γ-加成产物，而除了脂族硝基烯烃外，几乎仅产生α-加合物。在砜中存在OH功能的情况下（参见13），仅观察到（Z）γ加合物，而溴取代基则逆转了区域化学反应。