4-烯丙基-2-甲基吡咯烷 | 733752-87-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯烷类
• 中文名称: 4-烯丙基-2-甲基吡咯烷
• 中文别名: 吡咯烷,2-甲基-4-(2-丙烯-1-基)-
• 英文名称: 4-allyl-2-methyl-pyrrolidine
• 英文别名: 4-Allyl-2-methyl-pyrrolidin；2-Methyl-4-prop-2-enylpyrrolidine
• CAS: 733752-87-9
• 化学式: C₈H₁₅N
• mdl: MFCD19218120
• 分子量: 125.214
• InChiKey: PGDSQCNYLVEZFD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  9
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  12
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  4-烯丙基-2-甲基吡咯烷 在 [Me2Si(η5-C5Me4)(t-BuN)]U(NMe2)2 作用下， 以 氘代苯 为溶剂， 以100%的产率得到2,6-dimethyl-1-aza-norbornane
  参考文献：
  名称：

  Constrained Geometry Organoactinides as Versatile Catalysts for the Intramolecular Hydroamination/Cyclization of Primary and Secondary Amines Having Diverse Tethered C−C Unsaturation

  摘要：

  A series of "constrained geometry" organoactinide complexes, (CGC)An(NMe)(2) (CGC = Me2Si(eta(5)-Me4C5)((BuN)-Bu-t); An = Th, 1; U, 2), has been prepared via efficient in situ, two-step protodeamination routes in good yields and high purity. Both 1 and 2 are quantitatively converted to the neutrally charged, solvent-free dichlorides (1-Cl-2, 2-Cl-2) and slightly more soluble diiodides (1-I-2, 2-I-2) with excess Me3Si-X (X = Cl, I) in non-coordinating solvents. The new complexes were characterized by NMR spectroscopy, elemental analysis, and (for 1 and 2) single-crystal X-ray diffraction, revealing substantially increased metal coordinative unsaturation vs the corresponding Me2SiCp ''(2)AnR(2) (Cp '' = eta(5)-Me4C5; An = Th, R = CH2(SiMe3), 3; An = U, R = CH2Ph, 4) and Cp'(2)AnR(2) (Cp' = eta(5)-Me5C5 ; An = Th, R = CH2(SiMe3), 5; An = U, R = CH2(SiMe3), 6) complexes. Complexes 1-6 exhibit broad applicability for the intramolecular hydroamination of diverse C-C unsaturations, including terminal and internal aminoalkenes (primary and secondary amines), aminoalkynes (primary and secondary amines), aminoallenes, and aminodienes. Large turnover frequencies (N-t up to 3000 h(-1)) and high regioselectivities (>= 95%) are observed throughout, along with moderate to high diastereoselectivities (up to 90% trans ring closures). With several noteworthy exceptions, reactivity trends track relative 5f ionic radii and ancillary ligand coordinative unsaturation. Reactivity patterns and activation parameters are consistent with a reaction pathway proceeding via turnover-limiting CC/CC insertion into the An-N sigma-bond.

  DOI：

  10.1021/ja0665444
• 作为产物：
  描述：

  2-allylpent-4-en-1-amine 在 [Me2Si(η5-C5Me4)(t-BuN)]Th(NMe2)2 作用下， 以 氘代苯 为溶剂， 以95%的产率得到4-烯丙基-2-甲基吡咯烷
  参考文献：
  名称：

  Constrained Geometry Organoactinides as Versatile Catalysts for the Intramolecular Hydroamination/Cyclization of Primary and Secondary Amines Having Diverse Tethered C−C Unsaturation

  摘要：

  A series of "constrained geometry" organoactinide complexes, (CGC)An(NMe)(2) (CGC = Me2Si(eta(5)-Me4C5)((BuN)-Bu-t); An = Th, 1; U, 2), has been prepared via efficient in situ, two-step protodeamination routes in good yields and high purity. Both 1 and 2 are quantitatively converted to the neutrally charged, solvent-free dichlorides (1-Cl-2, 2-Cl-2) and slightly more soluble diiodides (1-I-2, 2-I-2) with excess Me3Si-X (X = Cl, I) in non-coordinating solvents. The new complexes were characterized by NMR spectroscopy, elemental analysis, and (for 1 and 2) single-crystal X-ray diffraction, revealing substantially increased metal coordinative unsaturation vs the corresponding Me2SiCp ''(2)AnR(2) (Cp '' = eta(5)-Me4C5; An = Th, R = CH2(SiMe3), 3; An = U, R = CH2Ph, 4) and Cp'(2)AnR(2) (Cp' = eta(5)-Me5C5 ; An = Th, R = CH2(SiMe3), 5; An = U, R = CH2(SiMe3), 6) complexes. Complexes 1-6 exhibit broad applicability for the intramolecular hydroamination of diverse C-C unsaturations, including terminal and internal aminoalkenes (primary and secondary amines), aminoalkynes (primary and secondary amines), aminoallenes, and aminodienes. Large turnover frequencies (N-t up to 3000 h(-1)) and high regioselectivities (>= 95%) are observed throughout, along with moderate to high diastereoselectivities (up to 90% trans ring closures). With several noteworthy exceptions, reactivity trends track relative 5f ionic radii and ancillary ligand coordinative unsaturation. Reactivity patterns and activation parameters are consistent with a reaction pathway proceeding via turnover-limiting CC/CC insertion into the An-N sigma-bond.

  DOI：

  10.1021/ja0665444

文献信息

• Paul; Cottin, Bulletin de la Societe Chimique de France, 1940, vol. <5> 7, p. 626,629
  作者：Paul、Cottin

  DOI：——

  日期：——
• Cottin, Comptes Rendus Hebdomadaires des Seances de l'Academie des Sciences, 1933, vol. 197, p. 254
  作者：Cottin

  DOI：——

  日期：——
• Constrained Geometry Organoactinides as Versatile Catalysts for the Intramolecular Hydroamination/Cyclization of Primary and Secondary Amines Having Diverse Tethered C−C Unsaturation
  作者：Bryan D. Stubbert、Tobin J. Marks

  DOI：10.1021/ja0665444

  日期：2007.4.1

  A series of "constrained geometry" organoactinide complexes, (CGC)An(NMe)(2) (CGC = Me2Si(eta(5)-Me4C5)((BuN)-Bu-t); An = Th, 1; U, 2), has been prepared via efficient in situ, two-step protodeamination routes in good yields and high purity. Both 1 and 2 are quantitatively converted to the neutrally charged, solvent-free dichlorides (1-Cl-2, 2-Cl-2) and slightly more soluble diiodides (1-I-2, 2-I-2) with excess Me3Si-X (X = Cl, I) in non-coordinating solvents. The new complexes were characterized by NMR spectroscopy, elemental analysis, and (for 1 and 2) single-crystal X-ray diffraction, revealing substantially increased metal coordinative unsaturation vs the corresponding Me2SiCp ''(2)AnR(2) (Cp '' = eta(5)-Me4C5; An = Th, R = CH2(SiMe3), 3; An = U, R = CH2Ph, 4) and Cp'(2)AnR(2) (Cp' = eta(5)-Me5C5 ; An = Th, R = CH2(SiMe3), 5; An = U, R = CH2(SiMe3), 6) complexes. Complexes 1-6 exhibit broad applicability for the intramolecular hydroamination of diverse C-C unsaturations, including terminal and internal aminoalkenes (primary and secondary amines), aminoalkynes (primary and secondary amines), aminoallenes, and aminodienes. Large turnover frequencies (N-t up to 3000 h(-1)) and high regioselectivities (>= 95%) are observed throughout, along with moderate to high diastereoselectivities (up to 90% trans ring closures). With several noteworthy exceptions, reactivity trends track relative 5f ionic radii and ancillary ligand coordinative unsaturation. Reactivity patterns and activation parameters are consistent with a reaction pathway proceeding via turnover-limiting CC/CC insertion into the An-N sigma-bond.