cis-(2S,5R)-2-methoxycarbonyl-5-(thien-2-yl)pyrrolidino[3,4:1,2][60]fullerene | 1195986-79-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 菲及其衍生物
• 英文名称: cis-(2S,5R)-2-methoxycarbonyl-5-(thien-2-yl)pyrrolidino[3,4:1,2][60]fullerene
• 英文别名: cis-2-methoxycarbonyl-5-(thien-2-yl)pyrrolidino[3,4:1,2][60]fullerene；(2S,5R)-2-methoxycarbonyl-5-(thien-2-yl)pyrrolidino[3,4:1,2][60]fullerene
• CAS: 1195986-79-8
• 化学式: C₆₈H₉NO₂S
• 分子量: 903.891
• InChiKey: CHUGHULLMZWPQP-NRTVDUQMSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  17.24
• 重原子数：
  72.0
• 可旋转键数：
  2.0
• 环数：
  34.0
• sp3杂化的碳原子比例：
  0.07
• 拓扑面积：
  38.33
• 氢给体数：
  1.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  cis-(2S,5R)-2-methoxycarbonyl-5-(thien-2-yl)pyrrolidino[3,4:1,2][60]fullerene 以 乙腈 为溶剂， 反应 168.0h， 以87%的产率得到
  参考文献：
  名称：

  Enantiospecific cis–trans Isomerization in Chiral Fulleropyrrolidines: Hydrogen-Bonding Assistance in the Carbanion Stabilization in H₂O@C₆₀

  摘要：

  The stereochemical outcome of cis-trans isomerization of optically pure [60], [70], and endohedral H2O@C60 fulleropyrrolidines reveals that the electronic nature of substituents, fullerene size, and surprisingly the incarcerated water molecule plays a crucial role in this rearrangement process. Theoretical DFT calculations are in very good agreement with the experimental findings. On the basis of the experimental results and computational calculations, a plausible reaction mechanism involving the hydrogen-bonding assistance of the inner water molecule in the carbanion stabilization of endofullerene is proposed.

  DOI：

  10.1021/ja5108854
• 作为产物：
  描述：

  2-((thiophen-2-ylmethylene)amino)acetic acid methyl ester 、 足球烯 在 (R)-FeSulPhos 、 copper diacetate 作用下， 以 甲苯 为溶剂， 反应 2.0h， 以45%的产率得到cis-(2S,5R)-2-methoxycarbonyl-5-(thien-2-yl)pyrrolidino[3,4:1,2][60]fullerene
  参考文献：
  名称：

  Enantiospecific cis–trans Isomerization in Chiral Fulleropyrrolidines: Hydrogen-Bonding Assistance in the Carbanion Stabilization in H₂O@C₆₀

  摘要：

  The stereochemical outcome of cis-trans isomerization of optically pure [60], [70], and endohedral H2O@C60 fulleropyrrolidines reveals that the electronic nature of substituents, fullerene size, and surprisingly the incarcerated water molecule plays a crucial role in this rearrangement process. Theoretical DFT calculations are in very good agreement with the experimental findings. On the basis of the experimental results and computational calculations, a plausible reaction mechanism involving the hydrogen-bonding assistance of the inner water molecule in the carbanion stabilization of endofullerene is proposed.

  DOI：

  10.1021/ja5108854

文献信息

• Stereodivergent Synthesis of Chiral Fullerenes by [3 + 2] Cycloadditions to C₆₀
  作者：Enrique E. Maroto、Salvatore Filippone、Margarita Suárez、Roberto Martínez-Álvarez、Abel de Cózar、Fernando P. Cossío、Nazario Martín

  DOI：10.1021/ja410408c

  日期：2014.1.15

  A wide range of new dipoles and catalysts have been used in 1,3-dipolar cycloadditions of N-metalated azomethine ylides onto C60 yielding a full stereodivergent synthesis of pyrrolidino[60]fullerenes with complete diastereoselectivities and very high enantioselectivities. The use of less-explored chiral α-iminoamides as starting 1,3-dipoles leads to an interesting double asymmetric induction resulting

  广泛的新型偶极子和催化剂已用于 N-金属化偶氮甲碱叶立德在 C60 上的 1,3-偶极环加成反应，产生具有完全非对映选择性和非常高对映选择性的吡咯烷 [60] 富勒烯的完全立体发散合成。使用较少探索的手性 α-亚氨基酰胺作为起始 1,3-偶极子导致有趣的双不对称诱导，导致匹配/错配效应，这取决于起始 α-亚氨基酰胺中立体中心的绝对构型。准对映体吡咯烷[60]富勒烯的质谱分析表明，在逆环加成反应中也发现了对映选择性过程。理论 DFT 计算与实验数据非常吻合。在此协议的基础上，提出了一个合理的反应机制。
• Switching the Stereoselectivity: (Fullero)Pyrrolidines “a la Carte”
  作者：Enrique E. Maroto、Salvatore Filippone、Angel Martín-Domenech、Margarita Suarez、Nazario Martín

  DOI：10.1021/ja306105b

  日期：2012.8.8

  Stereodivergent syntheses of cis/trans pyrrolidino[3,4:1,2]fullerenes and endo/exo pyrrolidines are reported with high enantioselectivity levels. Fullerenes are revealed as a useful benchmark to develop suitable catalysts to control the stereochemical outcome and to shed light on the mechanism involved in the related 1,3-dipolar cycloaddition.