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

• both within the context of a classic gold π-activation/protodeauration mechanism and a general acid-catalyzed mechanism without intermediate gold alkyls. Keywords: alkene hydroamination; general acid catalysis; gold catalysis; isotope effect; phosphine ligand effect; solvent effect; Introduction

• generally acidic conditions that initiate cyclization [34][35]. These observations are critical for informing future discussion and experiments related to this important reaction. Results Ligand effect To examine the catalytic activity of gold with ligands of different electronic properties, we used our

• observed rate was outside of one standard deviation from the average of 3 trials, confirming the overall reactivity trend. In hindsight, the ligand effect here may be expected to be small since the bisbiphenyl scaffold contains 2 of 3 identical substituents. Nevertheless, these comparisons confirm the

Diametric calix[6]arene-based phosphine gold(I) cavitands

• Gabriele Giovanardi,
• Andrea Secchi,
• Arturo Arduini and
• Gianpiero Cera

Beilstein J. Org. Chem. 2022, 18, 190–196, doi:10.3762/bjoc.18.21

• ’, 69%); ii) (Me2S)AuCl in DCM, 0 °C to rt (A’(AuCl), 94%; B’(AuCl), 92%; C’(AuCl), 96%). Ligand effect in gold(I)-catalyzed cycloisomerization of 1a. Supporting Information Supporting Information File 18: Experimental procedures, characterization data of compounds and copies of NMR spectra

Cobalt- and rhodium-catalyzed carboxylation using carbon dioxide as the C1 source

• Tetsuaki Fujihara and
• Yasushi Tsuji

Beilstein J. Org. Chem. 2018, 14, 2435–2460, doi:10.3762/bjoc.14.221

• carboxylative cyclization of ortho-substituted aromatic alkynes. Rh-catalyzed carboxylation of arylboronic esters 25. Rh-catalyzed carboxylation of alkenylboronic esters 27. Plausible reaction mechanism for the Rh-catalyzed carboxylation of arylboronic esters 25. Ligand effect on the Rh-catalyzed carboxylation

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

• Discussion Ligand effect of PyC in gold-catalyzed aromatic C–H arylation In this study, we selected the gold-catalyzed oxidative C–H arylation of arenes with arylsilanes [68][69], reported by Lloyd-Jones and Russell, to test the ligand effect of PyC (Table 1). Likely due to the low stability of electron-rich

• with a small amount of 3-arylbenzothiophene 3fa' (Table 2, entry 10). Reaction progress analysis To further unveil the ligand effect of PyC, time-production profiles of coupling product 3ba were investigated for the reaction of 1b and 2a with AuCl(PyC), AuCl(PPh3) and AuCl(IPr). The yield of 3ba was

Cu-catalyzed trifluoromethylation of aryl iodides with trifluoromethylzinc reagent prepared in situ from trifluoromethyl iodide

• Yuzo Nakamura,
• Motohiro Fujiu,
• Tatsuya Murase,
• Yoshimitsu Itoh,
• Hiroki Serizawa,
• Kohsuke Aikawa and
• Koichi Mikami

Beilstein J. Org. Chem. 2013, 9, 2404–2409, doi:10.3762/bjoc.9.277

• % loading of both CuI and phen ligand, the yield of 2a was further increased to a higher level (95% yield) along with an increased selectivity with only 2% yield of 3a (Table 1, entry 14). The ligand effect was further investigated in DMPU at 50 °C and phen was preferable to other diamine ligands (Table 2

Double N-arylation reaction of polyhalogenated 4,4’-bipyridines. Expedious synthesis of functionalized 2,7-diazacarbazoles

• Mohamed Abboud,
• Emmanuel Aubert and
• Victor Mamane

Beilstein J. Org. Chem. 2012, 8, 253–258, doi:10.3762/bjoc.8.26

• shown. (b) Space-filling views showing the channels along [010] in 3b (up) and [100] in 12c (down). Disordered solvent molecules occupying these channels are not shown. Cross-coupling reactions of bipyridines 2. Ligand effect in the double N-arylation of 2a with 6a. Functionalization of diazacarbazole

Triazole–Au(I) complex as chemoselective catalyst in promoting propargyl ester rearrangements

• Dawei Wang,
• Yanwei Zhang,
• Rong Cai and
• Xiaodong Shi

Beilstein J. Org. Chem. 2011, 7, 1014–1020, doi:10.3762/bjoc.7.115

• . Keywords: allene; chemoselectivity; gold catalysis; ligand effect; organometallic; Introduction The past decade has seen rapid growth in the use of homogeneous gold catalysis for conducting powerful organic transformations [1][2][3][4][5][6][7][8][9]. Like many other transition metal complexes, the

Intramolecular hydroamination of alkynic sulfonamides catalyzed by a gold–triethynylphosphine complex: Construction of azepine frameworks by 7-exo-dig cyclization

• Hideto Ito,
• Tomoya Harada,
• Hirohisa Ohmiya and
• Masaya Sawamura

Beilstein J. Org. Chem. 2011, 7, 951–959, doi:10.3762/bjoc.7.106

• effect of the counter anion of the cationic gold complex is shown in Table 1, entries 1 and 7–9. While OTf− was as effective as NTf2− (Table 1, entry 7), SbF6− and BF4− inhibited the reaction completely (Table 1, entries 8 and 9). The ligand effect is evaluated in Table 1, entries 1 and 10–14. The

• compounds. The protocol is applicable to the reaction of alkynic sulfonamides with an acyclic or ring-fused linker chain with various substitution patterns. Evaluation of the ligand effect in the gold catalysis with different ligands and substrates strongly suggested that the rate enhancement by the