Library-friendly synthesis of fluorinated ketones through functionalized hydration of alkynes and investigation of the reaction mechanism

Xu, Bo; Wang, Weibo; Hammond, Gerald B.

doi:10.1016/j.jfluchem.2011.05.006

Cited by 15 publications

(4 citation statements)

References 31 publications

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“…Electrospray ionization mass spectroscopy (ESI-MS) is a soft ionization technique, [17] and is an especially suitable technique, because cationic gold intermediates are charged species. In a previous work, we succeeded in detecting the existence of gold(III) species by using high-resolution (HR) ESI-MS. [18] First, we checked the HR ESI-MS spectra of sample 1 (Figure 4). We only detected the presence of various Au I species (e.g., [Au I -(Ph 3 P)] + (m/z 459.0571), [Au I (Ph 3 P)H 2 O] + (m/z 477.0677), [Au I -(Ph 3 P) 2 ] + (m/z 721.1483)).…”

Section: Resultsmentioning

confidence: 99%

“…Electrospray ionization mass spectroscopy (ESI‐MS) is a soft ionization technique,17 and is an especially suitable technique, because cationic gold intermediates are charged species. In a previous work, we succeeded in detecting the existence of gold(III) species by using high‐resolution (HR) ESI‐MS 18. First, we checked the HR ESI‐MS spectra of sample 1 (Figure 4).…”

Section: Resultsmentioning

confidence: 99%

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Alkyne/Alkene/Allene‐Induced Disproportionation of Cationic Gold(I) Catalyst

Kumar

Jasiński

Hammond

et al. 2014

Chemistry A European J

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The first detailed experimental study of the deactivation of cationic gold was conducted, and the influence of each component in the reaction system (substrate, counterion, solvent) on the decay process was examined. It was found that a substrate (alkyne/allene/alkene)-induced disproportionation of gold(I) may play a key role in the decay process. Our mechanism is supported by kinetic, XPS, voltammetry studies, and high-resolution ESI-MS data.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Alkyne/Alkene/Allene‐Induced Disproportionation of Cationic Gold(I) Catalyst

Kumar

Jasiński

Hammond

et al. 2014

Chemistry A European J

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“…Nevertheless, further experimental evidence was not often provided, and it was just postulated as a plausible mechanistic pathway. Even though Zhang and Toste were the first authors coming up with this idea, to the best of our knowledge, Hammond and Xu first confirmed this hypothesis through what they coined a gold-catalyzed “functionalized” hydrofluorination of alkynes in the presence of stoichiometric amounts of Selectfluor. , The reported one-pot tandem procedure provided access to α-substituted fluoroketones 247 and 248 in very good yields, albeit with moderate regioselectivity (Scheme ). Reaction conditions were applicable over a wide range of internal alkynes 246 and nonelectronically biased arylboronic acids.…”

Section: Fluorine In Oxidative Gold-catalyzed Reactionsmentioning

confidence: 99%

Fluorine and Gold: A Fruitful Partnership

2016

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Gold-catalyzed reactions have witnessed an exponential growth in the past decade. When the unique modes of activation exhibited by gold species meet species with either fluorinated building blocks or fluorinating reagents, new opportunities arise for the development of new methodologies in fluoroorganic chemistry. Indeed, gold and fluorine truly formed a very fruitful partnership, and different types of reactivity emerged from their combination. This review gives an overview of such endeavors. The special properties imparted by fluorine to organic molecules have been exploited in gold-catalyzed processes, allowing for the generation of unprecedented fluorinated chemical entities. Thus, the interaction of gold salts with fluorinated building blocks has been revised. In a second section, recent developments in gold-catalyzed nucleophilic fluorinations have been covered. The development of new gold catalysts that stabilize the Au-F bond as well as recent mechanistic studies in the field raised the interest of these types of methodologies for the generation of new C-F bonds. The use of electrophilic fluorine sources enabled new modes of gold catalysis. The incorporation of Selectfluor as an external oxidant constituted a new paradigm in gold chemistry, incorporating the elusive Au(I)/Au(III) redox couple in gold-catalyzed transformations. This strategy provided access to both new fluorinated chemical entities and nonfluorinated derivatives by means of coupling reactions. Those topics have been reviewed in the last two sections.

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“…Electrospray ionization mass spectroscopy (ESI-MS) is a soft ionization technique 96,97 and is an especially suitable technique because cationic gold intermediates are charged species. In a previous work we succeeded in detecting the existence of gold(III) species using high resolution-ESI-MS. 98 In this work first, we checked the high-resolution ESI-MS spectra of sample 1 ( Figure 9). We only detected the presence of various Au According to our previous studies of gold valence using ESI-MS, 93 Au III species are difficult to detect under standard condition, but we have been able to detect Au III species by adding a bidentate ligand and a halide (bipyridine and chloride).…”

Section: Resultsmentioning

confidence: 99%

Mechanistic insights and functionalization of alkynes in homogeneous gold catalysis.

Kumar¹

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Library-friendly synthesis of fluorinated ketones through functionalized hydration of alkynes and investigation of the reaction mechanism

Cited by 15 publications

References 31 publications

Alkyne/Alkene/Allene‐Induced Disproportionation of Cationic Gold(I) Catalyst

Alkyne/Alkene/Allene‐Induced Disproportionation of Cationic Gold(I) Catalyst

Fluorine and Gold: A Fruitful Partnership

Mechanistic insights and functionalization of alkynes in homogeneous gold catalysis.

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