Luqing Lin

The long-range deconjugative isomerization of a broad range of α,β-unsaturated amides, esters, and ketones by an in situ generated palladium hydride catalyst is described. This redox-economical process is triggered by a hydrometalation event and is thermodynamically driven by the refunctionalization of a primary or a secondary alcohol into an aldehyde or a ketone. Di-, tri-, and tetrasubstituted carbon-carbon double bonds react with similar efficiency; the system is tolerant toward a variety of

Reported is an achiral Cp^x Rh^III /chiral carboxylic acid catalyzed asymmetric C-H alkylation of diarylmethanamines with a diazomalonate, followed by cyclization and decarboxylation to afford 1,4-dihydroisoquinolin-3(2H)-one. Secondary alkylamines as well as nonprotected primary alkylamines underwent the transformation with high enantioselectivities (up to 98.5:1.5 e.r.) by using a newly developed chiral carboxylic acid as the sole source of chirality to achieve enantioselec

Enantioselective C(sp3)–H functionalization reactions using high-valent group 9 metal catalysts with cyclopentadienyl ligands have been achieved by the introduction of appropriate chiral carboxylic acids. However, the diversity of the chiral carboxylic acids, as well as that of the applicable substrate structures remains limited. Herein, we report pseudo-C2-symmetric tunable chiral carboxylic acids with a binaphthyl backbone and their application to enantioselective C(sp3)–H amidation reactions

We report here catalytic asymmetric iterative and domino cross-aldol reactions between aldehydes, endowed with a high level of robustness, flexibility, and generality. A Cu(I)-DTBM-SEGPHOS complex catalyzes an asymmetric cross-aldol reaction between acceptor aldehydes and boron enolates derived from donor aldehydes, which are generated through Ir-catalyzed isomerization of allyloxyboronates. The unit process can be repeated using the aldol products in turn as acceptor substrates for the subseque

Abstract Reported is an achiral Cp x Rh III /chiral carboxylic acid catalyzed asymmetric C−H alkylation of diarylmethanamines with a diazomalonate, followed by cyclization and decarboxylation to afford 1,4‐dihydroisoquinolin‐3( 2H )‐one. Secondary alkylamines as well as nonprotected primary alkylamines underwent the transformation with high enantioselectivities (up to 98.5:1.5 e.r.) by using a newly developed chiral carboxylic acid as the sole source of chirality to achieve enantioselective C−H

Herein, we report light-promoted photo/hydrogen atom transfer dual catalysis for arylsilylation of alkenes via the radical-radical cross-coupling with diverse hydrosilanes, which provides a simple and efficient method to prepare various organosilicon compounds with a wide range of substrate scope and good functional group tolerance under transition-metal- and chemical-oxidant-free conditions. Furthermore, the arylsilylation of alkenes can also proceed via the possible electron donor-acceptor com

Dip in! A Rh/dippf catalyst generates aldehyde-derived enol boranes at ambient temperature by isomerization of allyloxy- and homoallyloxyboranes. A one-pot isomerization/cross-aldol sequence provides aldehyde–aldehyde adducts in good yield with syn selectivity. Direct use of primary allylic and homoallylic alcohols was also achieved. The aldol reaction is one of the most fundamental carbon–carbon bond-forming reactions. A cross-aldol reaction between two different aldehydes, in principle, provid

Herein, we report visible light-promoted single nickel catalysis for diverse carbon-heteroatom couplings under mild conditions. This mild, general, and robust method to couple diverse nitrogen, oxygen, and sulfur nucleophiles with aryl(heteroaryl)/alkenyl iodides/bromides exhibits a wide functional group tolerance and is applicable to late-stage modification of pharmaceuticals and natural products. On the base of preliminary mechanistic studies, a Ni^I /Ni^III cycle via the g

Aryl halides are important chemical components in organic syntheses. Herein, we report visible-light-induced, single nickel-catalyzed halogen exchange of aromatic halides with the corresponding halide salts under mild conditions. Varieties of aryl iodides, bromides, and chlorides can smoothly undergo aromatic Finkelstein or retro-Finkelstein reactions with good functional group tolerance. Experimentally, mechanistic studies showed that excited-state NiII complexes for facile reductive eliminatio

Thiolates are known as the inhibitors of metal catalysis due to their strong coordination with the metal. Herein, we reported visible-light-induced homolysis of the Ni-S bond to activate the nickel(II) thiolates for the C-S coupling, obviating the use of exogenous photocatalysts and other additives. Various aryl bromides/iodides can efficiently couple with thiols with a wide range of functional groups under mild conditions. Preliminary mechanistic studies suggested the homolysis of the Ni-S bond

Abstract The widely used nickel catalysis for carbon‐heteroatom cross‐coupling reactions often requires high energy to achieve reductive elimination on Ni II complexes. To overcome the energy barrier of reductive elimination, the Ni II complexes often transform to Ni III facile reductive elimination via single electron transfer in photochemistry. Energy transfer to form the excited‐state Ni II complexes is feasible as well for carbon‐heteroatom couplings in nickel catalysis. This Review is focus

Sodium iodide facilitates halogen exchange in single nickel photocatalysis, which is critical to achieve C–N couplings of aryl chlorides and diverse nitrogen nucleophiles under visible-light irradiation in the absence of an exogenous photocatalyst.

Katalytischer Dip: Ein Rh/dippf-Katalysator überführt bei Umgebungstemperatur Aldehyde in Enolborane durch Isomerisierung von Allyloxy- und Homoallyloxyboranen. Eine Ein-Topf-Sequenz aus Isomerisierung und gekreuzter Aldolreaktion liefert die Addukte in guter Ausbeute mit syn-Selektivität. Auch primäre Allyl- und Homoallylalkohole konnten direkt eingesetzt werden. Detailed facts of importance to specialist readers are published as ”Supporting Information”. Such documents are peer-reviewed, but n

Photoinduced homolysis of Ni^II-carbon and -heteroatom bonds has been well studied for carbon-heteroatom couplings, but homolysis of the Ni^II-P bond is still undisclosed. Herein, we describe the homolysis of Ni^II-P bonds via ligand to metal charge transfer to access active nickel(I) complexes and phosphorus-centered radicals under visible-light irradiation for C-P couplings of diaryl phosphine oxides with aryl bromides. Experimental studies demonstrated that visib

The chemoselective generation of aldehyde-derived enolates to realize an aldehyde-aldehyde cross-aldol reaction is described. A combined Rh/dippf system efficiently promoted the isomerization/aldol sequence by using primary allylic, homoallylic, and bishomoallylic alcohols; secondary allylic and homoallylic alcohols; and trialkoxyboranes that were derived from primary allylic and homoallylic alcohols. The reaction proceeded at ambient temperature under base-free conditions, thus giving cross-ald