Novel radical tandem 1,6-enynes thioacylation/cyclization: Au-Pd nanoparticles catalysis versus thermal activation as a function of the substrate specificity

被引：5

作者：

Francesco, Irene Notar ^{[1
]}

Giauffret, Justine ^{[1
]}

Fontaine-Vive, Fabien ^{[1
]}

Edwards, Jennifer K. ^{[2
]}

Kiely, Christopher J. ^{[3
]}

Hutchings, Graham J. ^{[2
]}

Antoniotti, Sylvain ^{[1
]}

机构：

[1] Univ Nice Sophia Antipolis, CNRS, UMR 7272, Inst Chim Nice, F-06108 Nice 2, France

[2] Cardiff Univ, Sch Chem, Cardiff Catalysis Inst, Cardiff CF10 3AT, S Glam, Wales

[3] Lehigh Univ, Dept Mat Sci & Engn, Bethlehem, PA 18015 USA

来源：

TETRAHEDRON | 2014年 / 70卷 / 51期

关键词：

Cycloisomerisation; Nanocrystals; S-Nucleophile; Sustainable chemistry; Acetylthiyl radicals; GOLD NANOPARTICLES; THIYL RADICALS; BOND FORMATION; ALKYNES; CYCLIZATION; HYDROTHIOLATION; CARBOTHIOLATION; 1,5-ENYNES;

D O I：

10.1016/j.tet.2014.10.077

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

We studied the reactivity of 1,6-enynes with thioacetic acid (AcSH) under either thermal conditions or in the presence of catalytic amounts of supported Au or Au-Pd nanoparticles (NPs) under mild conditions. The 1,6-enynes undergo a tandem thioacylation/cyclization to original cyclic products featuring either a homoallylic thioester function or an enol thioester function depending on the substrate topology. Interestingly, the former process was found more efficient when performed in the presence of Au-Pd NPs while the latter process can be efficiently carried out under thermal conditions (100 degrees C). The reaction proceeds by a radical mechanism and the presence of precious metal NPs seems to stabilize the formation of free radical intermediates, as supported by experimental and theoretical results. (C) 2014 Elsevier Ltd. All rights reserved.

引用

页码：9635 / 9643

页数：9