Migratory insertion
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Ni-Catalyzed Regioselective 1,2-Dicarbofunctionalization of Olefins by Intercepting Heck Intermediates as Imine-Stabilized Transient Metallacycles Open
We disclose a strategy for Ni-catalyzed dicarbofunctionalization of olefins in styrenes by intercepting Heck C(sp3)-NiX intermediates with arylzinc reagents. This approach utilizes a readily removable imine as a coordinating group that pla…
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On the Nature of C(sp<sup>3</sup>)–C(sp<sup>2</sup>) Bond Formation in Nickel-Catalyzed Tertiary Radical Cross-Couplings: A Case Study of Ni/Photoredox Catalytic Cross-Coupling of Alkyl Radicals and Aryl Halides Open
The merger of photoredox and nickel catalysis has enabled the construction of quaternary centers. However, the mechanism, role of the ligand, and effect of the spin state for this transformation and related Ni-catalyzed cross-couplings inv…
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Transition-Metal-Catalyzed Functionalization of Alkynes with Organoboron Reagents: New Trends, Mechanistic Insights, and Applications Open
Catalytic functionalization of alkynes with organoboron reagents provides a straightforward access to stereochemically defined multisubstituted alkenes, which are structural motifs commonly found in bioactive compounds and organic material…
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Decarboxylative Hydroalkylation of Alkynes Open
The merger of open- and closed-shell elementary organometallic steps has enabled the selective intermolecular addition of nucleophilic radicals to unactivated alkynes. A range of carboxylic acids can be subjected to a CO(2) extrusion, nick…
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Synthesis of Diversely Functionalized Oxindoles Enabled by Migratory Insertion of Isocyanide to a Transient σ‐Alkylpalladium(II) Complex Open
Palladium‐catalyzed intramolecular carbopalladation of N‐aryl acrylamides followed by migratory insertion of an isocyanide‐coordinated C(sp 3 )−Pd intermediate afforded an alkylimidoyl−Pd II complex, which can be intercepted by a nucleophi…
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Uncommon carbene insertion reactions Open
Transition-metal-catalysed carbene insertion reaction is a straightforward and efficient protocol for the construction of carbon–carbon or carbon–heteroatom bonds.
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Excited-State Palladium-Catalyzed Radical Migratory Mizoroki–Heck Reaction Enables C2-Alkenylation of Carbohydrates Open
Excited-state palladium catalysis has emerged as a promising strategy for developing novel and valuable reactions. Herein, we report the first excited-state Pd-catalyzed 1,2-radical migratory Mizoroki-Heck reaction that enables C2-alkenyla…
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Ni(I)–Alkyl Complexes Bearing Phenanthroline Ligands: Experimental Evidence for CO <sub>2</sub> Insertion at Ni(I) Centers Open
Although the catalytic carboxylation of unactivated alkyl electrophiles has reached remarkable levels of sophistication, the intermediacy of (phenanthroline)Ni(I)-alkyl species-complexes proposed in numerous Ni-catalyzed reductive cross-co…
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Understanding a Hydroformylation Catalyst that Produces Branched Aldehydes from Alkyl Alkenes Open
This paper reports experimental and computational studies on the mechanism of a rhodium-catalyzed hydroformylation that is selective for branched aldehyde products from unbiased alkene substrates. This highly unusual selectivity relies on …
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Enantioselective Hydrothiolation: Diverging Cyclopropenes through Ligand Control Open
In this article, we advance Rh-catalyzed hydrothiolation through the divergent reactivity of cyclopropenes. Cyclopropenes undergo hydrothiolation to provide cyclopropyl sulfides or allylic sulfides. The choice of bisphosphine ligand dictat…
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N-Heterocyclic Carbene Based Nickel and Palladium Complexes: A DFT Comparison of the Mizoroki–Heck Catalytic Cycles Open
A theoretical investigation has been performed on nickel– and palladium–N-heterocyclic carbene (NHC) complexes in the Mizoroki–Heck (MH) reaction. A density functional theory (DFT) comparison of reaction pathways in cationic and neutral ca…
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Palladium(I) Dimer Enabled Extremely Rapid and Chemoselective Alkylation of Aryl Bromides over Triflates and Chlorides in Air Open
Disclosed herein is the first general chemo‐ and site‐selective alkylation of C−Br bonds in the presence of COTf, C−Cl and other potentially reactive functional groups, using the air‐, moisture‐, and thermally stable dinuclear Pd I catalys…
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Migratory Insertion of Carbenes into Au(III)–C Bonds Open
Migratory insertion of carbon-based species into transition-metal-carbon bonds is a mechanistic manifold of vast significance: it underlies the Fischer-Tropsch process, Mizoroki-Heck reaction, Ziegler-Natta and analogous late-transition-me…
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Heterogeneous Rhodium Single-Atom-Site Catalyst Enables Chemoselective Carbene N–H Bond Insertion Open
Transition-metal-catalyzed carbene insertion reactions of a nitrogen-hydrogen bond have emerged as robust and versatile methods for the construction of C-N bonds. While significant progress of homogeneous catalytic metal carbene N-H insert…
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Decarbonylative Fluoroalkylation at Palladium(II): From Fundamental Organometallic Studies to Catalysis Open
This Article describes the development of a decarbonylative Pd-catalyzed aryl-fluoroalkyl bond-forming reaction that couples fluoroalkylcarboxylic acid-derived electrophiles [RFC(O)X] with aryl organometallics (Ar-M'). This reaction was op…
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Chemoselective carbene insertion into the N−H bonds of NH3·H2O Open
The conversion of inexpensive aqueous ammonia (NH 3 ·H 2 O) into value-added primary amines by N−H insertion persists as a longstanding challenge in chemistry because of the tendency of Lewis basic ammonia (NH 3 ) to bind and inhibit metal…
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Palladium-Catalyzed Enantioselective Intermolecular Coupling of Phenols and Allylic Alcohols Open
An enantioselective intermolecular coupling of oxygen nucleophiles and allylic alcohols to give β-aryloxycarbonyl compounds is disclosed using a chiral pyridine oxazoline-ligated palladium catalyst under mild conditions. As opposed to the …
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Oxa- and Azabenzonorbornadienes as Electrophilic Partners under Photoredox/Nickel Dual Catalysis Open
Herein, the introduction of oxa- and azabenzonorbornadienes into photoredox/nickel dual catalysis in a regioselective and diastereoselective transformation is disclosed. The inherent advantages of this dual catalytic system allow the use o…
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Dioxygen insertion into the gold(<span>i</span>)–hydride bond: spin orbit coupling effects in the spotlight for oxidative addition Open
O 2 insertion into a Au( i )–H bond occurs through an oxidative addition/recombination mechanism that can only be described accurately by inclusion of spin orbit coupling (SOC) effects.
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Isolation of a Cu–H Monomer Enabled by Remote Steric Substitution of a <i>N</i>-Heterocyclic Carbene Ligand: Stoichiometric Insertion and Catalytic Hydroboration of Internal Alkenes Open
Transient Cu-H monomers have long been invoked in the mechanisms of substrate insertion in Cu-H catalysis. Their role from Cu-H aggregates has been mostly inferred since ligands to stabilize these monomeric intermediates for systematic stu…
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Migratory Insertion of CO into a Au–C Bond Open
A MeDalPhos-ligated gold(III) metallafluorene complex, generated via C-C oxidative addition of biphenylene, reacts with CO to produce 9-fluorenone. Experimental and computational studies show that this proceeds via a hitherto unknown migra…
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Asymmetric imino-acylation of alkenes enabled by HAT-photo/nickel cocatalysis Open
By merging nickel-mediated aza-Heck cyclization and HAT-photo-promoted acyl C–H activation, an unprecedented highly enantioselective imino-acylation of oxime ester-tethered alkenes with aldehydes as the acyl source has been developed.
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Rhodium-Catalyzed Hydrocarboxylation: Mechanistic Analysis Reveals Unusual Transition State for Carbon–Carbon Bond Formation Open
The mechanism of rhodium-COD-catalyzed hydrocarboxylation of styrene derivatives and α,β-unsaturated carbonyl compounds with CO2 has been investigated using density functional theory (PBE-D2/IEFPCM). The calculations support a catalytic cy…
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Room temperature olefination of methane with titanium–carbon multiple bonds Open
C–H activation of methane followed by dehydrocoupling at room temperature led ultimately to the formation of the olefin H2CCHtBu via the addition of redox-active ligands (L) such as thioxanthone or 2,2′-bipyridine (bipy) to (PNP)TiCHtBu(…
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Introducing the Catalytic Amination of Silanes via Nitrene Insertion Open
The direct functionalization of Si-H bonds by the nitrene insertion methodology is described. A copper(I) complex bearing a trispyrazolylborate ligand catalyzes the transfer of a nitrene group from PhI═NTs to the Si-H bond of silanes, disi…
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Investigation of Nitrile Hydration Chemistry by Two Transition Metal Hydroxide Complexes: Mn–OH and Ni–OH Nitrile Insertion Chemistry Open
Herein we describe the synthesis of a series of nickel complexes, including the formation of [(iPrPNHP)Ni(PMe3)][BPh4] (iPrPNHP = HN(CH2CH2(PiPr2))2). The ability of this phosphine complex to perform the 1,2-addition of H2O to produce the …
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Oxidative‐Insertion Reactivity Across a Geometrically Constrained Metal→Borane Interaction Open
While interest in cooperative reactivity of transition metals and Lewis acids is receiving significant attention, the scope of known reactions that directly exploit the polarized reverse‐dative σ‐bond of metal‐borane complexes (i.e., M → B…
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Palladium-catalyzed regiodivergent hydrochlorocarbonylation of alkenes for formation of acid chlorides Open
Novel strategy for acid chlorides formation that do not use carboxylic acids is particularly attractive in chemical synthesis but remains challenging. Herein, we reported the development of a highly effective Pd-catalyzed hydrochlorocarbon…
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Mechanistic Studies for Palladium Catalyzed Copolymerization of Ethylene with Vinyl Ethers Open
The mechanism of ethylene with vinyl ether (VE, CH2=CHOEt) copolymerization catalyzed by phosphine-sulfonate palladium complex (A) was investigated by density functional theory (DFT) calculation. On achieving an agreement between theory an…
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Reactive Palladium Carbenes: Migratory Insertion and Other Carbene–Hydrocarbyl Coupling Reactions on Well‐Defined Systems Open
Palladium complexes with carbene ligands are among the best known and more extensively used catalysts. Those carbenes are usually NHC or N , N ‐disubstituted derivatives and their use relies on the robust nature of the carbene ligands and …