Ligand effects, solvent cooperation, and large kinetic solvent deuterium isotope effects in gold(I)-catalyzed intramolecular alkene hydroamination

• Ruichen Lan,
• Brock Yager,
• Yoonsun Jee,
• Cynthia S. Day and
• Amanda C. Jones

Beilstein J. Org. Chem. 2024, 20, 479–496, doi:10.3762/bjoc.20.43

• Since the seminal 1998 report by Teles et al. on the gold(I)-catalyzed addition of alcohols to alkynes [1], a multitude of gold-catalyzed reactions have been reported. Great successes in mechanistic analysis and synthetic methods have been achieved for allene and alkyne activation, while the activation

• catalyzed by triflic acid and the gold π-activation pathway was questioned [26]. Nevertheless, advancements in gold-catalyzed reactions continued to be achieved. In particular, successful asymmetric methods were reported in short time after initially reported non-asymmetric methods, specifically Kojima’s

• electrophilic enough to activate alkenes toward the attack of pyrroles [34][35]. Gold-catalyzed reactions are known to be sensitive to subtle anion and media effects [48], and within the binary of rate determining π-activation versus protodeauration, trends do not always provide obvious conclusions. The unique

Heteroleptic metallosupramolecular aggregates/complexation for supramolecular catalysis

• Prodip Howlader and
• Michael Schmittel

Beilstein J. Org. Chem. 2022, 18, 597–630, doi:10.3762/bjoc.18.62

• gold-catalyzed reactions is still a concern, the catalytic transformation is often controlled by introducing a ligand as a first coordination sphere of the active gold species. In a supramolecular approach, introduction of the ligated gold complex inside a hollow cage may significantly improve the

Efficient [(NHC)Au(NTf₂)]-catalyzed hydrohydrazidation of terminal and internal alkynes

• Maximillian Heidrich and
• Herbert Plenio

Beilstein J. Org. Chem. 2020, 16, 2080–2086, doi:10.3762/bjoc.16.175

• catalysts with such ligands also display high activities in other gold-catalyzed reactions. Results and Discussion Catalyst screening: Five different [(NHC)Au(NTf2)] complexes 1, 2, 3, 4, and 5 with bulky NHC ligands were tested in the hydrohydrazidation of phenylacetylene with benzohydrazide (Scheme 2; T

AgNTf₂-catalyzed formal [3 + 2] cycloaddition of ynamides with unprotected isoxazol-5-amines: efficient access to functionalized 5-amino-1H-pyrrole-3-carboxamide derivatives

• Ziping Cao,
• Jiekun Zhu,
• Li Liu,
• Yuanling Pang,
• Laijin Tian,
• Xuejun Sun and
• Xin Meng

Beilstein J. Org. Chem. 2019, 15, 2623–2630, doi:10.3762/bjoc.15.255

• getting some insight into silver-carbene chemistry. The generation of α-imino gold carbene intermediates in gold-catalyzed reactions of alkynes has been widely studied in recent years [21][22][23][24][25][26][27][28][29][30]. In 2015, Ye and co-workers, as pioneers, developed this chemistry with the

Gold-catalyzed post-Ugi alkyne hydroarylation for the synthesis of 2-quinolones

• Xiaochen Du,
• Jianjun Huang,
• Anton A. Nechaev,
• Ruwei Yao,
• Jing Gong,
• Erik V. Van der Eycken,
• Olga P. Pereshivko and
• Vsevolod A. Peshkov

Beilstein J. Org. Chem. 2018, 14, 2572–2579, doi:10.3762/bjoc.14.234

• cyclizations of 7p–r required further optimization of the reaction conditions (Tables 2–4) and were complicated due the formation of regioisomeric products. After all, 2-quinolones 8p and 8q were isolated in good yields from gold-catalyzed reactions in hexafluoroisopropanol (HFIP), while 2-quinolone 8r was

Study on the synthesis of the cyclopenta[f]indole core of raputindole A

• Nils Marsch,
• Mario Kock and
• Thomas Lindel

Beilstein J. Org. Chem. 2016, 12, 334–342, doi:10.3762/bjoc.12.36

• which provided the hydrogenated tricyclic cyclopenta[f]indole core system in high yield. Keywords: gold-catalyzed reactions; heterocycles; indole alkaloids; natural products; synthesis; Introduction The raputindoles (1, raputindole A, Figure 1) from the rutaceous tree Raputia simulans Kallunki

Pyridylidene ligand facilitates gold-catalyzed oxidative C–H arylation of heterocycles

• Kazuhiro Hata,
• Hideto Ito,
• Yasutomo Segawa and
• Kenichiro Itami

Beilstein J. Org. Chem. 2015, 11, 2737–2746, doi:10.3762/bjoc.11.295

• -catalyzed reactions, phosphines, N-heterocyclic carbenes, pyridines and salen ligands have been applied as ligands for controlling the stability of catalysts, and chemo-, regio- and enantioselectivities of the reactions [31][32][33][34][35][36]. Recent advances in the gold-catalyzed reactions are

• elegant works of Lloyd-Jones and Russell on gold-catalyzed oxidative C–H arylation of simple arenes with arylsilanes have led the way to novel gold-catalyzed reactions that could not be achieved with other transition metals [68][69]. In these reactions, the oxidation of gold(I) to gold(III) is thought to

• arylation; gold catalysis; Introduction Over the past decade, gold salts and complexes have emerged as unique catalysts for the transformation of alkynes, alkenes and allenes [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19][20][21][22][23][24][25][26][27][28][29][30]. In most of the gold

Gold(I)-catalyzed enantioselective cycloaddition reactions

• Fernando López and
• José L. Mascareñas

Beilstein J. Org. Chem. 2013, 9, 2250–2264, doi:10.3762/bjoc.9.264

• intermediates Gold–carbene species are frequent intermediates in gold-catalyzed reactions, in particular those involving alkynes [33][34][35][36][37]. Gold(I) catalysts bind chemoselectively to C–C triple bonds, promoting the attack of different types of nucleophiles on these electrophilic species. Depending on

Gold(I)-catalyzed 6-endo hydroxycyclization of 7-substituted-1,6-enynes

• Ana M. Sanjuán,
• Alberto Martínez,
• Patricia García-García,
• Manuel A. Fernández-Rodríguez and
• Roberto Sanz

Beilstein J. Org. Chem. 2013, 9, 2242–2249, doi:10.3762/bjoc.9.263

• minor amounts of XI were also obtained [23] (Scheme 2). Following our interest in the development of new gold-catalyzed reactions [24][25][26][27][28][29][30][31], in this context we thought that it could be interesting to study if the cyclization of easily available compounds 1 bearing an internal

Gold-catalyzed glycosidation for the synthesis of trisaccharides by applying the armed–disarmed strategy

• Abhijeet K. Kayastha and
• Srinivas Hotha

Beilstein J. Org. Chem. 2013, 9, 2147–2155, doi:10.3762/bjoc.9.252

• hydrolysis and synthesis of a glycerol mannoside. Armed–disarmed effect in Ech-glycosides during gold-catalyzed reactions. Gold-catalyzed glycosidation at ambient temperature for the synthesis of trimannoside 25. Gold-catalyzed glycosidation at ambient temperature for the synthesis of higher saccharides

Acid, silver, and solvent-free gold-catalyzed hydrophenoxylation of internal alkynes

• Marcia E. Richard,
• Daniel V. Fraccica,
• Kevin J. Garcia,
• Erica J. Miller,
• Rosa M. Ciccarelli,
• Erin C. Holahan,
• Victoria L. Resh,
• Aakash Shah,
• Peter M. Findeis and
• Robert A. Stockland Jr.

Beilstein J. Org. Chem. 2013, 9, 2002–2008, doi:10.3762/bjoc.9.235

• is focused on the elimination of solvents and additives from the synthetic methodology [10]. Thus, the design of gold catalyzed reactions that proceed under solvent-free conditions and without the addition of silver salts or acidic promoters would be of interest to those charged with designing

Gold-catalyzed reaction of oxabicyclic alkenes with electron-deficient terminal alkynes to produce acrylate derivatives

• Yin-wei Sun,
• Qin Xu and
• Min Shi

Beilstein J. Org. Chem. 2013, 9, 1969–1976, doi:10.3762/bjoc.9.233

• temperature normally overnight. After complete consumption of the starting materials, monitored by TLC, the solvent was removed under reduced pressure and the residue was purified by flash column chromatography. Gold complexes used in this reaction. Gold-catalyzed reactions of oxabicyclic alkenes with

Gold-catalyzed cyclization of allenyl acetal derivatives

• Dhananjayan Vasu,
• Samir Kundlik Pawar and
• Rai-Shung Liu

Beilstein J. Org. Chem. 2013, 9, 1751–1756, doi:10.3762/bjoc.9.202

• one-pot procedure. We previously reported gold-catalyzed reactions of allenyl acetals with suitable dipolarophiles such as 1,3-diones to chemoselectively produce the cycloaddition product 2 [17] (Scheme 1). Similar reactions with nitrones stereoselectively delivered distinct formal cycloadducts 3 [18

Access to pyrrolo-pyridines by gold-catalyzed hydroarylation of pyrroles tethered to terminal alkynes

• Elena Borsini,
• Gianluigi Broggini,
• Andrea Fasana,
• Chiara Baldassarri,
• Angelo M. Manzo and
• Alcide D. Perboni

Beilstein J. Org. Chem. 2011, 7, 1468–1474, doi:10.3762/bjoc.7.170

• considerations, the N-propargyl amides of 1H-pyrrole-2-carboxylic acids 1a,b, easily prepared in high yields from the corresponding 1H-pyrrole-2-carboxylic acids and N-methyl-N-propargylamine with DCC as coupling reagent, were submitted to gold-catalyzed reactions under different conditions (Table 1). First, it

Directed aromatic functionalization

• Victor Snieckus

Beilstein J. Org. Chem. 2011, 7, 1215–1218, doi:10.3762/bjoc.7.141

• exception [32][33][34], to rationalize ortho selectivity. The aromatic ring annulative chemistry, which can be achieved by C–H-activation mediated processes, perhaps best exemplified by gold-catalyzed reactions [35][36], is astonishing and defies retrosynthetic analysis. While as yet mostly empirically

Efficient gold(I)/silver(I)-cocatalyzed cascade intermolecular N-Michael addition/intramolecular hydroalkylation of unactivated alkenes with α-ketones

• Ya-Ping Xiao,
• Xin-Yuan Liu and
• Chi-Ming Che

Beilstein J. Org. Chem. 2011, 7, 1100–1107, doi:10.3762/bjoc.7.126

• acid to activate unsaturated C–C bonds towards nucleophilic attack [1][2][3][4][5][6][7][8][9][10] (for selected reviews on gold-catalyzed reactions see [1][2][3][4][5][6][7][8][9]). Based on this mode of activation, several methods for the gold-catalyzed inter- and intramolecular addition of oxygen

Recent advances in the gold-catalyzed additions to C–C multiple bonds

• He Huang,
• Yu Zhou and
• Hong Liu

Beilstein J. Org. Chem. 2011, 7, 897–936, doi:10.3762/bjoc.7.103

• 2008 to the present. Keywords: asymmetric addition; catalysis; gold; C−C multiple bonds; tandem reaction; Review 1 Introduction Gold-catalyzed reactions have emerged as a powerful synthetic tool in modern organic synthesis. This past decade has been the boom time for homogeneous gold catalysis, which

• was rather limited in organic synthesis until the advantages of gold complexes as catalysts were discovered [1]. In comparison to other transition-metal catalysts, most gold-catalyzed reactions are atom-economic, remarkably mild with regard to reaction conditions, and most importantly, have a

• reviews have summarized well the progress of gold-catalyzed reactions up to 2008 [6][7][8][9][10][11][12][13][14][15][16]. Since then, the expansion of this field has continued unabated as evidenced by more than 500 publications to be found in the literature. Herein, we summarize the new research efforts

When gold can do what iodine cannot do: A critical comparison

• Sara Hummel and
• Stefan F. Kirsch

Beilstein J. Org. Chem. 2011, 7, 847–859, doi:10.3762/bjoc.7.97

• domino processes, for which gold pre-catalysts were found to be outstandingly effective, were paralleled by employing iodine electrophiles in place of gold compounds. This review highlights how, in certain cases, iodonium activation can match gold-catalyzed reactions to construct identical product

• transformed into diverse product classes, depending on whether gold or iodonium activation was used to trigger the transformation. Since a comprehensive discussion on gold catalysis is not intended, the following examples of gold-catalyzed reactions simply illustrate certain prototype reactivity that i) is

Au(I)/Au(III)-catalyzed Sonogashira-type reactions of functionalized terminal alkynes with arylboronic acids under mild conditions

• Deyun Qian and
• Junliang Zhang

Beilstein J. Org. Chem. 2011, 7, 808–812, doi:10.3762/bjoc.7.92

• was observed under the above conditions. Taking into account the counter ion effects in gold-catalyzed reactions [33][34][35], Ph3PAuOTf, produced from a combination of Ph3PAuCl and AgOTf in a 1:1 ratio, was investigated. To our delight, the expected product 2a could be isolated in 56% yield (Table 1

A comparative study of the Au-catalyzed cyclization of hydroxy-substituted allylic alcohols and ethers

• Berenger Biannic,
• Thomas Ghebreghiorgis and
• Aaron Aponick

Beilstein J. Org. Chem. 2011, 7, 802–807, doi:10.3762/bjoc.7.91

• sensitive functional groups. While cyclization reactions of highly elaborated substrates are desirable, mild chemoselective methods are necessary for this endeavor. Homogeneous gold-catalyzed reactions have emerged as a powerful new methodology for the construction of a diverse array of molecular

Solvent- and ligand-induced switch of selectivity in gold(I)-catalyzed tandem reactions of 3-propargylindoles

• Estela Álvarez,
• Delia Miguel,
• Patricia García-García,
• Manuel A. Fernández-Rodríguez,
• Félix Rodríguez and
• Roberto Sanz

Beilstein J. Org. Chem. 2011, 7, 786–793, doi:10.3762/bjoc.7.89

• tandem gold-catalyzed reactions of 3-propargylindoles initiated by 1,2-indole migrations, a selection of substrates 1a–i, bearing a methyl group at one of the propargylic positions and different (hetero)aromatic groups at both the other propargylic and terminal positions, were reacted under the

Synthetic applications of gold-catalyzed ring expansions

• David Garayalde and
• Cristina Nevado

Beilstein J. Org. Chem. 2011, 7, 767–780, doi:10.3762/bjoc.7.87

• starting from allenyl cyclobutanols [23]. 1.2 Cyclopropylmethanols Cyclopropyl methanols can be used, alternatively, as pre-electrophiles in gold-catalyzed reactions. In 2008 Chan and co-workers developed an efficient synthetic route to pyrrolidines via a tandem amination/ring expansion of these substrates

A racemic formal total synthesis of clavukerin A using gold(I)-catalyzed cycloisomerization of 3-methoxy-1,6-enynes as the key strategy

• Jae Youp Cheong and
• Young Ho Rhee

Beilstein J. Org. Chem. 2011, 7, 740–743, doi:10.3762/bjoc.7.84

• developed by us [15]. This reaction provides cycloheptane frameworks in a unique manner and illustrates the utility of the gold-catalyzed reactions [16][17][18][19][20][21][22][23]. From a retrosynthetic point of view, we envisioned two different approaches to the key enone intermediate 1 [3] to clavukerin

When cyclopropenes meet gold catalysts

• Frédéric Miege,
• Christophe Meyer and
• Janine Cossy

Beilstein J. Org. Chem. 2011, 7, 717–734, doi:10.3762/bjoc.7.82

• in a variety of gold-catalyzed reactions. The different contributions in this growing research area are summarized in this review. Keywords: cyclopropenes; gold carbenes; gold catalysis; gold-stabilized allylic cations; ring-opening; Review Introduction Homogeneous gold catalysis has become a

• bonds [1][2][3][4][5][6][7][8][9][10][11][12][13][14]. Whereas alkynes, alkenes and allenes have been widely used as substrates or partners in gold-catalyzed reactions, it was only rather recently, in 2008, that cyclopropenes entered the field of gold catalysis despite their well-known high and

• versatile reactivity in transition metal-catalyzed reactions [15]. As has been observed with other transition metals, the reactivity of cyclopropenes A in gold-catalyzed reactions is essentially (but not exclusively) related to their ability to act as ligands for π-acidic gold complexes, and hence, to

Construction of cyclic enones via gold-catalyzed oxygen transfer reactions

• Leping Liu,
• Bo Xu and
• Gerald B. Hammond

Beilstein J. Org. Chem. 2011, 7, 606–614, doi:10.3762/bjoc.7.71

• Leping Liu Bo Xu Gerald B. Hammond Department of Chemistry, University of Louisville, 2320 South Brook Street, Louisville, KY 40292, USA 10.3762/bjoc.7.71 Abstract During the last decade, gold-catalyzed reactions have become a tour de force in organic synthesis. Recently, the gold-, Brønsted acid

• this century, organic chemists became aware that gold salts or complexes were highly active catalysts in homogeneous catalysis because of the strong π- and σ-electrophilicity of gold [28][29][30][31][32][33]. Since then, the number of new gold-catalyzed reactions reported in the literature has