Rh-Catalyzed Cycloaddition of C60 with Enynes: Unveiling the Mechanistic Pathway

被引：4

作者：

Castanyer, Cristina ^{[1
]}

Artigas, Albert ^{[1
]}

Insa-Carreras, Nil ^{[1
]}

Sola, Miquel ^{[1
]}

Pla-Quintana, Anna ^{[1
]}

Roglans, Anna ^{[1
]}

机构：

[1] Univ Girona UdG, Inst Quim Computac & Catalisi IQCC, Dept Quim, Fac Ciencies, C-Maria Aurelia Capmany 69, Girona 17003, Catalunya, Spain

来源：

ADVANCED SYNTHESIS & CATALYSIS | 2024年 / 366卷 / 04期

关键词：

Cycloaddition; 1,6-enynes; Fullerene; Rhodium; Density Functional Calculations; PAUSON-KHAND REACTION; SINGLET OXYGEN; ENE REACTION; ALDER REACTION; BASIS-SETS; 1,6-ENYNES; CYCLOISOMERIZATION; FULLERENES; ALKYNES; RHODIUM;

D O I：

10.1002/adsc.202301189

中图分类号：

O69 [应用化学];

学科分类号：

081704 ;

摘要：

In this study we present a method for functionalizing C-60 through a Rh-catalyzed cyclization reaction with 1,6-enynes, resulting in the formation of a fused bicyclic structure. Additionally, fullerene derivatives are further functionalized through regioselective photooxygenation reactions. Our DFT calculations reveal two distinct reaction pathways: one involving rhodium-catalyzed cycloisomerization of the enyne followed by Diels-Alder with C-60, and the other featuring a rhodium-catalyzed [2+2+2] cycloaddition of enyne and C(60 )followed by isomerization. Surprisingly, both pathways exhibit nearly identical energy barriers. However, experimental tests indicate that the predominant pathway varies depending on the substitution motifs of the substrates. image

引用

页码：862 / 869

页数：8

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