Cyclization of 1,6-Enynes Catalyzed by Gold Nanoparticles Supported on TiO2: Significant Changes in Selectivity and Mechanism, as Compared to Homogeneous Au-Catalysis

被引：54

作者：

Gryparis, Charis ^{[1
]}

Efe, Christina ^{[1
]}

Raptis, Christos ^{[1
]}

Lykakis, Ioannis N. ^{[1
]}

Stratakis, Manolis ^{[1
]}

机构：

[1] Univ Crete, Dept Chem, Iraklion 71003, Greece

来源：

ORGANIC LETTERS | 2012年 / 14卷 / 12期

关键词：

SKELETAL REORGANIZATION; TRIPLE BONDS; GOLD(I)-CATALYZED CYCLOISOMERIZATION; ENYNES; ALKYNES; REARRANGEMENT; PLATINUM; CLEAVAGE; CYCLOADDITION; SPECTROSCOPY;

D O I：

10.1021/ol301212j

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Gold nanoparticles supported on TiO2 (1.2 mol %) catalyze, for the first time under heterogeneous conditions, the cycloisomerization of a series of 1,6-enynes in high yields. In several cases, the product selectivity differs significantly as compared to homogeneous Au(I)-catalysis. Based on product analysis and stereoisotopic studies it is proposed that the major or exclusive pathway involves a 5-exo cyclization mode to form stereoselectively gold cyclopropyl carbenes that undergo a single cleavage pathway, in contrast to homogeneous Au-catalysis where the double cleavage pathway operates substantially.

引用

页码：2956 / 2959

页数：4

共 4 条

[1] Investigation of the Cycloisomerization of 1,6-Enynes Catalyzed by Gold Nanoparticles with First-Principles Calculations: Mechanism and Selectivity
Tang, Dianyong
Chen, Zhongzhu
Tang, Ying
Zhang, Jin
Xu, Zhigang
Zhang, Jinsheng
JOURNAL OF PHYSICAL CHEMISTRY C, 2014, 118 (32): : 18510 - 18520
[2] Novel radical tandem 1,6-enynes thioacylation/cyclization: Au-Pd nanoparticles catalysis versus thermal activation as a function of the substrate specificity
Francesco, Irene Notar
Giauffret, Justine
Fontaine-Vive, Fabien
Edwards, Jennifer K.
Kiely, Christopher J.
Hutchings, Graham J.
Antoniotti, Sylvain
TETRAHEDRON, 2014, 70 (51) : 9635 - 9643
[3] Nickel-catalyzed defluorinative asymmetric cyclization of Trifluoromethyl-substituted 1,6-Enynes: Insights from DFT calculations on the reaction mechanism and selectivity
Zhang, Qiang
Wang, Jinzhao
Zhu, Rongxiu
Zhang, Dongju
MOLECULAR CATALYSIS, 2024, 564
[4] Steric tuning of C2-symmetric chiral N-heterocyclic carbene in gold-catalyzed asymmetric cyclization of 1,6-enynes
Yamada, Ken-ichi
Matsumoto, Yasumasa
Selim, Khalid B.
Yamamoto, Yasutomo
Tomioka, Kiyoshi
TETRAHEDRON, 2012, 68 (22) : 4159 - 4165

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