Highly Selective Gold-Catalyzed Arene Synthesis

Hashmi, A. Stephen K.; Frost, and Tanja M.; Bats, Jan W.

doi:10.1021/ja005570d

Cited by 783 publications

(367 citation statements)

References 21 publications

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“…In 2000 my research group discovered the gold catalyzed isomerization of furans 38 which possess alkynyl groups to the corresponding highly substituted and anellated arenes 39 (40). Alkyl, aryl (41) and alkynyl substituents are tolerated.…”

Section: C-c-bond Formationmentioning

confidence: 99%

Homogeneous gold catalysts and alkynes: A successful liaison

2003

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The use of the combination of homogeneous gold-catalysts and alkynes in organic synthesis is reviewed from its beginnings in C-N-bond formation to the newest developments in C-C-bond formation. The common basic principle of these reactions is discussed. Special attention is devoted to the question where the gold catalysts are superior to either other catalysts or more traditional synthetic approaches to the product molecules.Transition metal catalysis has become one of the most important tools in organic synthesis. It allowed entirely new transformations which were not possible previously by "traditional" organic reactions and thus significantly increased the efficiency of synthesis. It also made retrosynthetic analysis more demanding as many of the transformations go along with a remarkable increase in molecular complexity (1) which makes the relationship between the product and the starting material more difficult to recognize. In many of these reactions, especially in the case of late transition metals, C-C multiple bonds in either alkenes or alkynes, are the site of reaction. Theoretical backgroundIn the field of homogeneous gold catalysis the alkynes 1, which have the structural motive of a C-C-triple bond, belong to the most popular substrates. The reason for that popularity is the high reactivity of the alkynes which originates from their electronic structure (2). Often the corresponding alkenes with their C-C-double bond are less reactive.On one hand, the alkynes possess two orthogonal -orbitals high in energy occupied by two electrons each. These react with electrophilic reagents (E) like halogens in organic synthesis or electrophilic metal centers like gold (in the oxidation states I or III) in the field of transition metal catalysis (3,4). In the interaction with a metal center both the -orbital in the plane of metal co-ordination and theorbital perpendicular to it are able to interact with the dorbitals of the metal.On the other hand, the lowest unoccupied orbital of the alkynes is low in energy and thus eagerly react with strong nucleophiles like for example ethyne 2 with catalytical amounts of alkoholates in the Reppe synthesis of vinyl ethers 3 (5).Most unfortunately, weak nucleophiles (Nu) do not react directly with the alkynes, although this is often desired in organic synthesis. But the alkyne can be activated by co-ordination to the electrophilic gold complexes as mentioned above. This co-ordination withdraws electron

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Section: C-c-bond Formationmentioning

confidence: 99%

Homogeneous gold catalysts and alkynes: A successful liaison

2003

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“…Cationic phosphine Au(I) species were found to be excellent catalysts in the addition of alcohols to alkynes in 1998 [14]. Subsequently, gold(III) complexes were investigated as catalysts and used in the synthesis of five-membered rings with two heteroatoms [15][16][17][18]. Several years later, R 3 PAuX (X = trifluoromethanesulphonate, OTf − ) or other weakly coordinating counter ions) demonstrated excellent catalytic performance in Conia-ene [19,20] and hydroarylation [21][22][23] reactions, as well as several carbon-heteroatom bond-forming reactions [24][25][26].…”

Section: Introductionmentioning

confidence: 99%

Highly Efficient One-Pot Synthesis of 2,4-Disubstituted Thiazoles Using Au(I) Catalyzed Oxidation System at Room Temperature

Wang

Líu

2016

Catalysts

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Abstract:In the present work, gold complex catalysts with Mor-DalPhos ligands were successfully prepared using mesylates as counter ions. Seven ammonium sulfonates were synthesized to promote the production of intermediate sulfonyloxymethyl ketone. It was found that low-acidity N,N-dimethylbenzenaminium methanesulfonate showed excellent activity in the reaction. Furthermore, the catalysts effectively avoided the loss of activity due to the low acidity. Various thioamides were directly added to the resulting reaction mixture without the separation of intermediate product. Then, twenty kinds of 2,4-disubstituted thiazoles were efficiently synthesized at room temperature with the highest yield of 91%. This work provides an efficiency and mild gold-catalyzed oxidation system for the one-pot synthesis of thiazole and its derivatives.

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“…218 This transformation is initiated by the phenol synthesis previously described by the same author. 219 This well stablished reaction gives in this particular case an o-(alkynyl)phenol that cyclizes in situ in the presence of the gold-catalyst to yield the corresponding benzofurans in moderate to good yields. Intermediate o-(alkynyl)phenols are observed as minor products in these reactions, which is attributed to the deactivation of the catalyst before the cyclization is completed.…”

Section: Five-and Seven-membered Ringsmentioning

confidence: 93%

1,3-Dien-5-ynes: Versatile Building Blocks for the Synthesis of Carbo- and Heterocycles

et al. 2016

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ABSTRACT:1,3-Dien-5-ynes have been extensively used as starting materials for the synthesis of a wide number of different carbo-and heterocycles. The aim of this review is to give an overview of their utility in organic synthesis, highlighting the variety of compounds that can be directly accessed from single reactions over these systems. Thus, cycloaromatization processes are initially commented, followed by reactions directed towards the syntheses of five-membered rings, other carbocycles and, finally, heterocycles. The diverse methodologies that have been developed for the synthesis of each of these types of compounds from 1,3-dien-5-ynes are presented, emphasizing the influence of the reaction conditions and the use of additional reagents in the outcome of the transformations.2

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Highly Selective Gold-Catalyzed Arene Synthesis

Cited by 783 publications

References 21 publications

Homogeneous gold catalysts and alkynes: A successful liaison

Homogeneous gold catalysts and alkynes: A successful liaison

Highly Efficient One-Pot Synthesis of 2,4-Disubstituted Thiazoles Using Au(I) Catalyzed Oxidation System at Room Temperature

1,3-Dien-5-ynes: Versatile Building Blocks for the Synthesis of Carbo- and Heterocycles

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