富勒烯二聚体中吡咯并吡唑啉环连接的竞争反环加成反应。

Competitive retro-cycloaddition reaction in fullerene dimers connected through pyrrolidinopyrazolino rings.

机构信息

Departamento de Química Orgánica, Facultad de Ciencias Químicas, Universidad Complutense de Madrid, E-28040, Madrid, Spain.

出版信息

J Org Chem. 2009 Nov 6;74(21):8174-80. doi: 10.1021/jo901644b.

DOI:10.1021/jo901644b

PMID:19785423

Abstract

Competitive retro-cycloaddition in [60]- and [70]fullerene homodimers (1a,1c) as well as [60]/[70]heterodimer (1b), linked through 2-pyrazolinopyrrolidino bridges, has been studied by means of HPLC, mass spectrometry, and theoretical calculations at the density functional theory (DFT) level by using the two-layered ONIOM approach. The results of these investigations indicate that the retro-cycloaddition reaction of pyrrolidinofullerenes is favored compared to the retro-cycloaddition reaction of 2-pyrazolinofullerenes in compounds 1a-c. Evidence of the occurrence of this process have been observed both by HPLC and MS-MALDI, these findings being in good agreement with those predicted by theoretical calculations.

摘要

[60]-和[70]富勒烯同二聚体（1a、1c）以及通过 2-吡唑啉基吡咯烷桥连接的[60]/[70]富勒烯杂二聚体（1b）的竞争反环加成反应已通过高效液相色谱法、质谱法和理论计算进行了研究，密度泛函理论（DFT）水平采用两层 ONIOM 方法。这些研究结果表明，与化合物 1a-c 中的 2-吡唑啉富勒烯的反环加成反应相比，吡咯烷富勒烯的反环加成反应更有利。通过 HPLC 和 MS-MALDI 都观察到了这个过程的发生，这些发现与理论计算的预测结果非常吻合。