2-烯丙基-2-硝基环己酮 | 100820-08-4

• 分子结构分类: 有机化合物 - 有机1,3-偶极化合物 - 烯丙基型1,3-偶极有机化合物
• 中文名称: 2-烯丙基-2-硝基环己酮
• 英文名称: 2-allyl-2-nitrocyclohexanone
• 英文别名: 2-nitro-2-prop-2-enylcyclohexan-1-one
• CAS: 100820-08-4
• 化学式: C₉H₁₃NO₃
• 分子量: 183.207
• InChiKey: AKLLFNRZLHJDEF-UHFFFAOYSA-N

物化性质

• 沸点：
  288.0±29.0 °C(Predicted)
• 密度：
  1.11±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  13
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  62.9
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2-烯丙基-2-硝基环己酮 在 Raney Ni (W₇) sodium hydroxide 、 lithium aluminium tetrahydride 、 重铬酸吡啶 、 9-borabicyclo[3.3.1]nonane dimer 、 氢气 、 双氧水 、 对甲苯磺酸 作用下， 以 四氢呋喃 、 甲醇 、 乙醚 、 苯 为溶剂， 30.0 ℃ 、10.13 MPa 条件下， 反应 344.5h， 生成 (5R)-7,10-dioxa-4-azadispiro[4.0.46.45]tetradecane
  参考文献：
  名称：

  Enantioselective Allylation of Nitro Group-Stabilized Carbanions Catalyzed by Chiral Crown Ether Phosphine−Palladium Complexes

  摘要：

  Enantioselective allylations of alpha-nitro ketones (3) and alpha-nitro esters (15) with allyl acetate were carried out in the presence of 2 equiv of alkali metal fluorides (KF, RbF, CsF) and 1 mol % of palladium catalysts prepared in situ from Pd-2(dba)(3) . CHCl3 and chiral phosphine ligands. Moderate enantioselectivities were observed in the reaction of nitro ketones 3, giving products 4 (4a, 49% ee; 4b, 58% ee; 4c, 44% ee) when rubidium fluoride and ferrocenylphosphine ligands bearing monoaza-15-crown-5 (Ib) or monoaza-18-crown-6 (Ic) moieties were used as a base and a chiral ligand, respectively. Optically active allylation product 4a was converted into 1-methyl-1-azaspiro[4.5]-decan-10-amine (13), a precursor to opioid receptor binding agents. Enantioselectivity in the reaction of nitro esters 15 increased in accord with increasing steric demand of the ester alkyl group (Me < Et < t-Bu). The highest selectivity (80% eel for the reaction of tert-butyl ester 15c was observed when the reaction was carried out at -40 degrees C in the presence of the palladium catalyst with the ligand (Ic) bearing a monoaza-18-crown-6 moiety, RbF (2 equiv), and RbClO4 (1 equiv). The pronounced effect of the crown ether moiety for both enantioselection and rate acceleration can be explained by assuming the formation of a ternary complex involving the crown ether, rubidium cation, and enolate anion at the stereodifferentiating transition state. Optically active nitro ester (R)-16c was converted into (R)-alpha-methylglutamic acid (20).

  DOI：

  10.1021/jo961343b
• 作为产物：
  描述：

  碳酸丙烯乙酯 、 2-硝基环己酮 在 四(三苯基膦)钯 作用下， 以 四氢呋喃 为溶剂， 反应 0.17h， 以90%的产率得到2-烯丙基-2-硝基环己酮
  参考文献：
  名称：

  Ognyanov, Vassil I.; Hesse, Manfred, Synthesis, 1985, # 6/7, p. 645 - 647

  摘要：

  DOI：

文献信息

• Reluctant Cross-Metathesis Reactions: The Highly Beneficial Effect of Microwave Irradiation
  作者：Yoann Coquerel、Jean Rodriguez、Antoine Michaut、Thomas Boddaert

  DOI：10.1055/s-2007-983825

  日期：2007.9

  The beneficial effect of microwave irradiation versus classical thermal conditions is demonstrated through a series of comparative cross-metathesis reactions.

  微波辐射相对于传统热条件的有益效果通过一系列比较的交叉转烯反应得以证明。
• OGNYANOV, V. I.;HESSE, M., SYNTHESIS, BRD, 1985, N 6-7, 645-647
  作者：OGNYANOV, V. I.、HESSE, M.

  DOI：——

  日期：——
• Ognyanov, Vassil I.; Hesse, Manfred, Synthesis, 1985, # 6/7, p. 645 - 647
  作者：Ognyanov, Vassil I.、Hesse, Manfred

  DOI：——

  日期：——
• Enantioselective Allylation of Nitro Group-Stabilized Carbanions Catalyzed by Chiral Crown Ether Phosphine−Palladium Complexes
  作者：Masaya Sawamura、Yuki Nakayama、Wen-Ming Tang、Yoshihiko Ito

  DOI：10.1021/jo961343b

  日期：1996.1.1

  Enantioselective allylations of alpha-nitro ketones (3) and alpha-nitro esters (15) with allyl acetate were carried out in the presence of 2 equiv of alkali metal fluorides (KF, RbF, CsF) and 1 mol % of palladium catalysts prepared in situ from Pd-2(dba)(3) . CHCl3 and chiral phosphine ligands. Moderate enantioselectivities were observed in the reaction of nitro ketones 3, giving products 4 (4a, 49% ee; 4b, 58% ee; 4c, 44% ee) when rubidium fluoride and ferrocenylphosphine ligands bearing monoaza-15-crown-5 (Ib) or monoaza-18-crown-6 (Ic) moieties were used as a base and a chiral ligand, respectively. Optically active allylation product 4a was converted into 1-methyl-1-azaspiro[4.5]-decan-10-amine (13), a precursor to opioid receptor binding agents. Enantioselectivity in the reaction of nitro esters 15 increased in accord with increasing steric demand of the ester alkyl group (Me < Et < t-Bu). The highest selectivity (80% eel for the reaction of tert-butyl ester 15c was observed when the reaction was carried out at -40 degrees C in the presence of the palladium catalyst with the ligand (Ic) bearing a monoaza-18-crown-6 moiety, RbF (2 equiv), and RbClO4 (1 equiv). The pronounced effect of the crown ether moiety for both enantioselection and rate acceleration can be explained by assuming the formation of a ternary complex involving the crown ether, rubidium cation, and enolate anion at the stereodifferentiating transition state. Optically active nitro ester (R)-16c was converted into (R)-alpha-methylglutamic acid (20).