(R)-6-nitro-6-(2'-propenyl)-1,4-dioxaspiro[4,5]decane | 185054-48-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (R)-6-nitro-6-(2'-propenyl)-1,4-dioxaspiro[4,5]decane
• 英文别名: (6R)-6-nitro-6-prop-2-enyl-1,4-dioxaspiro[4.5]decane
• CAS: 185054-48-2
• 化学式: C₁₁H₁₇NO₄
• 分子量: 227.26
• InChiKey: TUEAHYQQPJAKAX-JTQLQIEISA-N

物化性质

• 沸点：
  333.5±37.0 °C(Predicted)
• 密度：
  1.17±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  16
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.82
• 拓扑面积：
  64.3
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (R)-6-nitro-6-(2'-propenyl)-1,4-dioxaspiro[4,5]decane 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 作用下， 以 四氢呋喃 、 甲醇 、 乙醚 为溶剂， 30.0 ℃ 、10.13 MPa 条件下， 反应 176.5h， 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：

  2-烯丙基-2-硝基环己酮 、 乙二醇 在 对甲苯磺酸 作用下， 以 苯 为溶剂， 反应 168.0h， 以36%的产率得到(R)-6-nitro-6-(2'-propenyl)-1,4-dioxaspiro[4,5]decane
  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

文献信息

• 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).