On the Functionalization of C60 with Vinylallenes Generated in situ by Rhodium Catalysis

IF 4.4 2区化学 Q2 CHEMISTRY, APPLIED

Advanced Synthesis & Catalysis Pub Date : 2024-10-06 DOI:10.1002/adsc.202401163

Cristina Castanyer, Albert Artigas, Miquel Solà, Anna Pla-Quintana, Anna Roglans

引用次数: 0

Abstract

The functionalization of fullerenes is important for several reasons, primarily related to enhancing their chemical reactivity, solubility, and potential of applications in optoelectronics and biomedicine. In this study, we present a novel approach to functionalize C60 through a cascade process encompassing an unprecedented Rh-catalyzed cycloisomerization of 1,6-allenynes to in situ generate a vinylallene that is followed by a Diels-Alder reaction with pristine fullerene, resulting in the formation of 6,6-fused bicyclic fullerene derivatives. The mechanism governing this process was elucidated by DFT calculations and confirmed by deuterium labelling and control experiments, demonstrating the critical role of traces of water in the reaction medium to mediate the observed reactivity.

查看原文本刊更多论文

铑催化原位生成的乙烯基烯烃对 C60 的官能化作用

富勒烯的功能化有几个重要原因，主要与提高其化学反应活性、溶解性以及在光电子学和生物医学中的应用潜力有关。在本研究中，我们提出了一种通过级联过程对 C60 进行功能化的新方法，该过程包括前所未有的 1,6-allenynes 在 Rh 催化下环状异构化以原位生成乙烯基烯，然后与原始富勒烯发生 Diels-Alder 反应，最终形成 6,6 熔合双环富勒烯衍生物。通过 DFT 计算阐明了这一过程的机理，并通过氘标记和控制实验进行了确认，证明了反应介质中的微量水在介导所观察到的反应性方面的关键作用。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

求助全文

约1分钟内获得全文求助全文

来源期刊

Advanced Synthesis & Catalysis 化学-应用化学

CiteScore

9.40

自引率

7.40%

发文量

447

审稿时长

1.8 months

期刊介绍： Advanced Synthesis & Catalysis (ASC) is the leading primary journal in organic, organometallic, and applied chemistry. The high impact of ASC can be attributed to the unique focus of the journal, which publishes exciting new results from academic and industrial labs on efficient, practical, and environmentally friendly organic synthesis. While homogeneous, heterogeneous, organic, and enzyme catalysis are key technologies to achieve green synthesis, significant contributions to the same goal by synthesis design, reaction techniques, flow chemistry, and continuous processing, multiphase catalysis, green solvents, catalyst immobilization, and recycling, separation science, and process development are also featured in ASC. The Aims and Scope can be found in the Notice to Authors or on the first page of the table of contents in every issue.