Mechanism of the N-protecting group dependent annulations of 3-aryloxy alkynyl indoles under gold catalysis: a computational study

被引：19

作者：

Cheng, Bing ^{[1
]}

Huang, Genping ^{[1
]}

Xu, Liang ^{[1
]}

Xia, Yuanzhi ^{[1
]}

机构：

[1] Wenzhou Univ, Coll Chem & Mat Engn, Wenzhou 325035, Peoples R China

来源：

ORGANIC & BIOMOLECULAR CHEMISTRY | 2012年 / 10卷 / 22期

基金：

中国国家自然科学基金;

关键词：

EFFECTIVE CORE POTENTIALS; STEREOCONTROLLED TOTAL-SYNTHESIS; MOLECULAR CALCULATIONS; 1-(1-ALKYNYL)CYCLOPROPYL KETONES; INTERMOLECULAR REACTIONS; CANNABIMIMETIC INDOLES; CLAISEN REARRANGEMENT; SUBSTITUTED FURANS; PLATINUM CATALYSIS; PROTON-TRANSFER;

D O I：

10.1039/c2ob25316j

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

The mechanism of the gold-catalyzed annulations of 3-aryloxy alkynyl indoles developed by Tu et al. was studied by DFT calculations. It was found that both indole derivatives of electron-donating and electron-withdrawing protective groups would first undergo the 5-exo-dig cyclization simultaneously upon activation by cationic [PR3Au+] species. However, divergent reactivity of the resulting spirocyclic intermediate in competitive 1,2-alkenyl migration and nucleophilic water addition reactions towards C3 was predicted. When protected by electron-donating group, the 1,2-alkenyl migration occurs to generate a tricyclic intermediate, from which an aromatic Claisen rearrangement/nucleophilic addition sequence results in the observed 1,2-phenoxy migration. In case of electron-withdrawing group, the 1,2-alkenyl migration would be unfavorable. Instead, the nucleophilic addition of water oxygen to C3 is more facile, and leads to the hemiketal intermediate. The possible roles of water-cluster and OTf anion as proton shuttles in both reactions were also evaluated.

引用

页码：4417 / 4423

页数：7

共 153 条

[31] Mechanism of the gold(L)-catalyzed Rautenstrauch rearrangement:: A center-to-helix-to-center chirality transfer [J].

Faza, ON ;

López, CS ;

Alvarez, R ;

de Lera, AR .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2006, 128 (07) :2434-2437

[32] Gold-catalyzed intramolecular reaction of indoles with alkynes: Facile formation of eight-membered rings and an unexpected allenylation [J].

Ferrer, C ;

Echavarren, AM .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2006, 45 (07) :1105-1109

[33] Intra- and intermolecular reactions of indoles with alkynes catalyzed by gold [J].

Ferrer, Catalina ;

Amijs, Catelijne H. M. ;

Echavarren, Antonio M. .

CHEMISTRY-A EUROPEAN JOURNAL, 2007, 13 (05) :1358-1373

[34] Synthesis of the tetracyclic core skeleton of the lundurines by a gold-catalyzed cyclization [J].

Ferrer, Catalina ;

Escribano-Cuesta, Ana ;

Echavarren, Antonio M. .

TETRAHEDRON, 2009, 65 (44) :9015-9020

[35] A cationic cyclisation route to prenylated indole alkaloids: synthesis of malbrancheamide B and brevianamide B, and progress towards stephacidin A [J].

Frebault, Frederic C. ;

Simpkins, Nigel S. .

TETRAHEDRON, 2010, 66 (33) :6585-6596

[36]

Frisch M. J., 2016, Gaussian 03 Revision B.03

[37] Catalytic carbophilic activation:: Catalysis by platinum and gold π acids [J].

Fuerstner, Alois ;

Davies, Paul W. .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2007, 46 (19) :3410-3449

[38] Gold and platinum catalysis-a convenient tool for generating molecular complexity [J].

Fuerstner, Alois .

CHEMICAL SOCIETY REVIEWS, 2009, 38 (11) :3208-3221

[39] Chemistry and biology of roseophilin and the prodigiosin alkaloids:: A survey of the last 2500 years [J].

Fürstner, A .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2003, 42 (31) :3582-3603

[40] Gold-Catalyzed Regioselective Hydration of Propargyl Acetates Assisted by a Neighboring Carbonyl Group: Access to α-Acyloxy Methyl Ketones and Synthesis of (±)-Actinopolymorphol B [J].

Ghosh, Nayan ;

Nayak, Sanatan ;

Sahoo, Akhila K. .

JOURNAL OF ORGANIC CHEMISTRY, 2011, 76 (02) :500-511

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