| 185054-58-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯烷类
• CAS: 185054-58-4
• 化学式: C₁₃H₂₂N₂O₃
• 分子量: 254.329
• InChiKey: FRZSXMUYLYVMBX-CYBMUJFWSA-N

物化性质

• 沸点：
  362.4±44.0 °C(Predicted)
• 密度：
  1.18±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.55
• 重原子数：
  18.0
• 可旋转键数：
  2.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.85
• 拓扑面积：
  51.13
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  在 lithium aluminium tetrahydride 、 N,N'-二环己基碳二亚胺 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 30.0h， 生成 (2R,5'R)-N-(1'-methyl-1'-azaspiro[4,5]dec-6-yl)-2-methoxy-2-phenylacetamide
  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：

  (R)-6-nitro-6-(2'-propenyl)-1,4-dioxaspiro[4,5]decane 在 Raney Ni (W₇) 吡啶 、 盐酸 、 sodium hydroxide 、 lithium aluminium tetrahydride 、 重铬酸吡啶 、 9-borabicyclo[3.3.1]nonane dimer 、 氢气 、 双氧水 、 三乙胺 作用下， 以 四氢呋喃 、 甲醇 、 乙醚 、 二氯甲烷 为溶剂， 30.0 ℃ 、10.13 MPa 条件下， 反应 219.5h， 生成
  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