(-)-4-endo-Amino-2-oxabicyclo[3.3.0]oct-7-en-3-one | 174742-36-0

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: (-)-4-endo-Amino-2-oxabicyclo[3.3.0]oct-7-en-3-one
• 英文别名: (3S,3aR,6aR)-3-amino-3,3a,4,6a-tetrahydrocyclopenta[b]furan-2-one
• CAS: 174742-36-0
• 化学式: C₇H₉NO₂
• 分子量: 139.154
• InChiKey: FOYAMRCAKRZJQQ-JKUQZMGJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0
• 重原子数：
  10
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  52.3
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (-)-4-endo-Amino-2-oxabicyclo[3.3.0]oct-7-en-3-one 在 四(三苯基膦)钯 三甲基氯硅烷 、 碳酸氢钠 、 六甲基二硅氮烷 作用下， 以 四氢呋喃 为溶剂， 反应 25.5h， 生成 (2S)-2-[(1S,4R)-4-(2,4-dioxopyrimidin-1-yl)cyclopent-2-en-1-yl]-2-(phenylmethoxycarbonylamino)acetic acid
  参考文献：
  名称：

  Aggarwal, Varinder K.; Monteiro, Nuno, Journal of the Chemical Society. Perkin transactions I, 1997, # 17, p. 2531 - 2537

  摘要：

  DOI：
• 作为产物：
  描述：

  (3S,3aR,6aR)-3a,4-dihydro-3-hydroxy-3H-cyclopenta[b]furan-2(6aH)-one 在 sodium azide 、 三苯基膦 、 zinc dibromide 、 偶氮二甲酸二乙酯 作用下， 以 四氢呋喃 、 二甲基亚砜 为溶剂， 反应 24.5h， 生成 (-)-4-endo-Amino-2-oxabicyclo[3.3.0]oct-7-en-3-one
  参考文献：
  名称：

  Scope and Limitations in Palladium-Catalyzed Substitution Reactions of Unsaturated Fused Lactones

  摘要：

  The palladium-catalyzed nucleophilic substitution of C-4-substituted 2-oxabicyclo[3.3.0]oct-7-en-3-ones (unsaturated, fused lactones) have been studied particularly in relation to how electronic and steric factors influenced the rate and efficiency of substitution reactions. Thus, a range of a-substituted lactones were prepared (X = H, Me, OH, OAc, Br, N-3, NHCBZ) and subjected to palladium-catalyzed substitution reaction with diethyl sodiomalonate, and it was found that reaction rates increased with increasing electron-withdrawing ability of the substituent and that there was a strong correlation between rate and pK(a) of the corresponding substituted acetic acids (XCH2-CO2H). The only exception to the correlation was with X = OH, in which case the endo isomer reacted considerably faster than expected and the exo isomer reacted much slower than expected. It was also found that the rates of reaction of the endo isomers were greater than the exo isomers. The increased rates have been accounted for by a shift in equilibrium between the lactone and the pi-allyl palladium intermediate toward the latter species due to the increased stability of the carboxylate (electronic effects) or relief of steric hindrance in the starting lactone. The scope and limitations of the palladium-catalyzed substitution reaction were studied by reacting a range of lactones with a range of nucleophiles. Lactones with unactivated leaving groups such as 2 (X = H) coupled efficiently with good nucleophiles such as malonate but only poorly with less reactive nucleophiles such as azide. Lactones with activated leaving groups such as 4a (X = OH) coupled efficiently with a broad range of nucleophiles.

  DOI：

  10.1021/jo962106b

文献信息

• Design, Synthesis, and 1,3-Dipolar Cycloaddition of (5<i>R</i>)- [and (5<i>S</i>)]-5,6-Dihydro-5-phenyl-2<i>H</i>-1,4-oxazin-2-one <i>N</i>-Oxides as Chiral (<i>E</i>)-Geometry-Fixed α-Alkoxycarbonylnitrones
  作者：Osamu Tamura、Kentoku Gotanda、Jun Yoshino、Yasuhiro Morita、Romi Terashima、Mayumi Kikuchi、Tsutomu Miyawaki、Naka Mita、Masayuki Yamashita、Hiroyuki Ishibashi、Masanori Sakamoto

  DOI：10.1021/jo000903a

  日期：2000.12.1

  Optically pure (5R)- [and (5S)]-5,6-dihydro-5-phenyl-2H-1, 4-oxazin-2-one N-oxides [(5R)- and (5S)-2] were designed as chiral (E)-geometry-fixed alpha-alkoxycarbonylnitrones 1. The nitrones (5R)- and (5S)-2 were synthesized by three-step oxidation of (R)- and (S)-phenylglycinols [(R)- and (S)-3], condensation of the resulting (R)- and (S)-2-hydroxylamino-2-phenylethanols [(R)- and (S)-5] with glyoxylic

  光学纯的（5R）-[和（5S）]-5,6-二氢-5-苯基-2H-1、4-恶嗪-2-一N-氧化物[（5R）-和（5S）-2]为设计为手性（E）-几何固定的α-烷氧基羰基硝酮1.硝酮（5R）-和（5S）-2是通过（R）-和（S）-苯基甘氨醇[[R]-和（S）-3]，将所得的（R）-和（S）-2-羟基氨基-2-苯基乙醇[[R]-和（S）-5]与乙醛酸缩合，并将中间体硝基环化（R）-和（S）-6b。硝酮（5R）-2在温和条件下与烯烃7-14反应，通过对空间要求最低的exo模式提供相应的环加合物15-22作为主要产物。从（5S）-2和环戊二烯获得的Cycloadduct 30被有效地修饰为（1S，4S，5R）-4-苄氧基羰基氨基-2-氧杂双环[3.3.0] oct-7-en-3-one（28），
• Scope and Limitations in Palladium-Catalyzed Substitution Reactions of Unsaturated Fused Lactones
  作者：Varinder K. Aggarwal、Nuno Monteiro、Gary J. Tarver、Ray McCague

  DOI：10.1021/jo962106b

  日期：1997.7.1

  The palladium-catalyzed nucleophilic substitution of C-4-substituted 2-oxabicyclo[3.3.0]oct-7-en-3-ones (unsaturated, fused lactones) have been studied particularly in relation to how electronic and steric factors influenced the rate and efficiency of substitution reactions. Thus, a range of a-substituted lactones were prepared (X = H, Me, OH, OAc, Br, N-3, NHCBZ) and subjected to palladium-catalyzed substitution reaction with diethyl sodiomalonate, and it was found that reaction rates increased with increasing electron-withdrawing ability of the substituent and that there was a strong correlation between rate and pK(a) of the corresponding substituted acetic acids (XCH2-CO2H). The only exception to the correlation was with X = OH, in which case the endo isomer reacted considerably faster than expected and the exo isomer reacted much slower than expected. It was also found that the rates of reaction of the endo isomers were greater than the exo isomers. The increased rates have been accounted for by a shift in equilibrium between the lactone and the pi-allyl palladium intermediate toward the latter species due to the increased stability of the carboxylate (electronic effects) or relief of steric hindrance in the starting lactone. The scope and limitations of the palladium-catalyzed substitution reaction were studied by reacting a range of lactones with a range of nucleophiles. Lactones with unactivated leaving groups such as 2 (X = H) coupled efficiently with good nucleophiles such as malonate but only poorly with less reactive nucleophiles such as azide. Lactones with activated leaving groups such as 4a (X = OH) coupled efficiently with a broad range of nucleophiles.
• Aggarwal, Varinder K.; Monteiro, Nuno, Journal of the Chemical Society. Perkin transactions I, 1997, # 17, p. 2531 - 2537
  作者：Aggarwal, Varinder K.、Monteiro, Nuno

  DOI：——

  日期：——