ConspectusComputational chemistry has become an established tool for the study of origins chemical phenomena and examination molecular properties. Because major advances in theory, hardware software, calculations processes can nowadays be done with reasonable accuracy on a time-scale that is competitive or even faster than experiments. This overview will highlight broad applications computational organic organometallic reactivities, including catalytic (NHC-, Cu-, Pd-, Ni-catalyzed)...

Olefin shuffle for just a nickel Controlling the geometry of carbon-carbon double bonds is central component chemical manufacturing. One useful trick to shift hydrogen atoms around interconvert C=C isomers selectively. However, this approach typically requires precious metals. Kapat et al. now report that more-abundant can catalyze rapid conversion terminal olefins into internal with high selectivity trans geometry. The odd-electron complex relies on radical mechanism shuttle carbon from...

Although machine learning bears enormous potential to accelerate developments in homogeneous catalysis, the frequent need for extensive experimental data can be a bottleneck implementation. Here, we report an unsupervised workflow that uses only five points. It makes use of generalized parameter databases are complemented with problem-specific silico acquisition and clustering. We showcase power this strategy challenging problem speciation palladium (Pd) catalysts, which mechanistic...

Abstract Building on our recent disclosure of catalysis at dinuclear Pd I sites, we herein report the application this concept to realization first catalytic method convert aryl iodides into corresponding ArSeCF 3 compounds. Highly efficient CSeCF coupling a range was achieved, enabled by an air‐, moisture‐, and thermally stable catalyst. The novel SeCF ‐bridged complex isolated, studied for its competence shown be recoverable. Experimental computational data are presented in support catalysis.

The reduction of Pd(II) intermediates to Pd(0) is a key elementary step in vast number Pd-catalyzed processes, ranging from cross-coupling, C-H activation, Wacker chemistry. For one the most powerful new generation phosphine ligands, PtBu3, oxidation state Pd(I), and not Pd(0), generated upon Pd(II). mechanism Pd(I) has been investigated by means experimental computational studies for formation highly active precatalyst {Pd(μ-Br)(PtBu3)}2. dinuclear as opposed complex, (tBu3P)2Pd was shown...

Disclosed herein is the first general chemo- and site-selective alkylation of C-Br bonds in presence COTf, C-Cl other potentially reactive functional groups, using air-, moisture-, thermally stable dinuclear Pd

Pharmaceutically relevant methylene oxindoles are synthesized by a palladium(0)-catalyzed intramolecular chlorocarbamoylation reaction of alkynes. A relatively underexplored class caged phosphine ligands is uniquely suited for this transformation, enabling high levels reactivity and exquisite trans selectivity. This report entails the first transition-metal-catalyzed atom-economic addition carbamoyl chloride across an alkyne.

A mechanistic study of the Pd-catalyzed intramolecular addition carbamoyl chlorides and aryl halides across alkynes is presented.

We report the mild activation of carbamoyl azides to corresponding nitrenes using a blue light/[Ir]-catalyzed strategy, which enables stereospecific access N-trifluoromethyl imidazolidinones and benzimidazolones. These novel structural motifs proved be highly robust, allowing their downstream diversification. On basis our combined computational experimental studies, we propose that an electron rebound with excited metal catalyst is undergone, involving reduction-triggered nitrogen loss,...

We report a highly robust, general and stereoselective method for the synthesis of 3-(chloromethylene)oxindoles from alkyne-tethered carbamoyl chlorides using PdCl2(PhCN)2 as catalyst. The transformation involves stereo- regioselective chloropalladation an internal alkyne to generate nucleophilic vinyl PdII species, which then undergoes intramolecular cross-coupling with chloride. reaction proceeds under mild conditions, is insensitive presence moisture air, readily scalable. products...

S-aryl phosphorothioates are privileged motifs in pharmaceuticals, agrochemicals, and catalysts; yet, the challenge of devising a straightforward synthetic route to enantioenriched has remained unsolved date. We demonstrate herein first direct C-SP(=O)(OR')(OR'') coupling diverse chiral phosphorothioate salts with aryl iodides, enabled by an air- moisture-stable Pd

Owing to the unknown correlation of a metal’s ligand and its resulting preferred speciation in terms oxidation state, geometry, nuclearity, rational design multinuclear catalysts remains challenging. With goal accelerate identification suitable ligands that form trialkylphosphine-derived dihalogen-bridged Ni(I) dimers, we herein employed an assumption-based machine learning approach. The workflow offers guidance space for desired without (or only minimal) prior experimental data points. We...

Abstract The ever increasing demands for greater sustainability and lower energy usage in chemical processes call fundamentally new approaches reactivity principles. In this context, the pronounced prevalence of odd-oxidation states less precious metals bears untapped potential distinct modes via metalloradical catalysis 1–3 . Contrary to well-established paradigm that organic free radicals, upon addition a vinylcyclopropane, lead rapid ring opening under strain release—a transformation...

Abstract Aufbauend auf unseren jüngsten Entdeckungen bei zweikernigen Pd I ‐Komplexen beschreiben wir hier die Anwendung dieses Konzeptes zur Realisierung der ersten katalytischen Umwandlung von Aryliodiden zu ArSeCF 3 ‐Verbindungen. Durch Verwendung eines luft‐, feuchtigkeits‐ und temperaturbeständigen ‐Zweikernkomplexes konnte hoch effiziente C‐SeCF ‐Kupplung einer Reihe erreicht werden. Ein neuer SeCF ‐verbrückter zweikerniger ‐Komplex wurde isoliert, seine katalytische Kompetenz...

Abstract Disclosed herein is the first general chemo‐ and site‐selective alkylation of C−Br bonds in presence COTf, C−Cl other potentially reactive functional groups, using air‐, moisture‐, thermally stable dinuclear Pd I catalyst, [Pd(μ‐I)PtBu 3 ] 2 . The bromo‐selectivity independent substrate relative positioning competing reaction sites, as such fully predictable. Primary secondary alkyl chains were introduced with extremely high speed (<5 min time) at room temperature under...

Abstract We report a new air‐stable Pd I dimer, [Pd(μ‐I)(PCy 2 t Bu)] , which triggers E ‐selective olefin migration to enamides and styrene derivatives in the presence of multiple functional groups with complete tolerance air. The same dimer also extremely rapid C−C coupling (alkylation arylation) at room temperature modular triply selective fashion aromatic C−Br, C−OTf/OFs, C−Cl bonds poly(pseudo)halogenated arenes, displaying superior activity over previous generations for substrates that...

Contrary to the general belief that Pd-catalyzed cross-coupling at sites of severe steric hindrance are disfavored, we herein show oxidative addition C-Br ortho an adamantyl group is as favored corresponding adamantyl-free system due attractive dispersion forces. This enabled development a fully selective arylation and alkylation group, even if challenged with competing non-hindered C-OTf or C-Cl sites. The method makes use air-stable PdI dimer enables straightforward access diversely...

Computational studies receive increased attention in the mechanistic exploration of transition metal catalyzed reactions. Especially Pd catalysis, numerous insights could be gained by use computational tools to complement experimental order provide a more detailed picture. This includes not only novel scenarios, but also comparison different plausible reaction pathways. The current intense calculations Pd‐catalyzed reactions has encouraged constant advancements field. However, number...

Abstract Eine intramolekulare Palladium(0)‐katalysierte Chlorcarbamoylierung von Alkinen zur Synthese pharmazeutisch relevanter Methylenoxindole wird beschrieben. Dabei eine weitgehend unerforschte Klasse Phosphanliganden verwendet, die sich als besonders geeignet für diese Umwandlung herausstellte und sowohl hohe Reaktivität auch ausschließliche trans ‐Selektivität ermöglicht. Dieser Bericht zeigt erste übergangsmetallkatalysierte atomeffiziente Addition eines Carbamoylchlorids an ein Alkin.

The application of air- and moisture-stable dinuclear palladium(I) complex [Pd(μ-I)(P<i>t</i>-Bu₃)]₂ as an efficient catalyst for the Heck cross-coupling reaction aryl iodides bromides with acrylates styrenes is described. developed protocol robust operationally simple shows a high functional-group tolerance. employed dimer highly under these nucleophilic well elevated-temperature conditions, allowing its recovery after completion recycling.

Abstract Dinuclear Pd I complexes have found widespread applications as diverse catalysts for a multitude of transformations. Initially their ability to function pre‐catalysts low‐coordinated 0 species was harnessed in cross‐coupling. Such dimers are inherently labile and relatively sensitive oxygen. In recent years, more stable dinuclear −Pd frameworks, which feature bench‐stability robustness towards nucleophiles well recoverability reactions, were explored shown trigger privileged...

While the TeCF3 moiety features promising properties and potential in a range of applications, no direct synthetic method exists for its incorporation into aromatic scaffolds. This report first catalytic formation C(sp2 )-TeCF3 bonds. The relies on Pd/Xantphos system allows trifluoromethyltellurolation aryl iodides. Our computational experimental mechanistic analyses shed light privileged activity Xantphos this transformation.