Organolanthanides are highly efficient catalysts for inter- and intramolecular hydroamination of various C-C unsaturations such as alkenes, alkynes, allenes, dienes. Attractive features organolanthanide include very high turnover frequencies excellent stereoselectivities, rendering this methodology applicable to concise synthesis naturally occurring alkaloids other polycyclic azacycles. The general mechanism involves turnover-limiting multiple bond insertion into the Ln-N bond, followed by...

C2-symmetric bis(oxazolinato)lanthanide complexes of the type [(4R,5S)-Ph2Box]La[N(TMS)2]2, [(4S,5R)-Ar2Box]La[N(TMS)2]2, and [(4S)-Ph-5,5-Me2Box]La[N(TMS)2]2 (Box = 2,2'-bis(2-oxazoline)methylenyl; Ar 4-tert-butylphenyl, 1-naphthyl; TMS SiMe3) serve as precatalysts for efficient enantioselective intramolecular hydroamination/cyclization aminoalkenes aminodienes. These new catalyst systems are conveniently generated in situ from known metal precursors Ln[N(TMS)2]3 or Ln[CH(TMS)2]3 (Ln La,...

Novel chiral dinuclear Co(II)-salen catalysts self-assembled through the pyridone/aminopyridine hydrogen-bonding pair have been developed. The Co(II)-Salen catalyst results in significant rate acceleration (48 times faster rate) as well excellent enantioselectivity (96% ee vs 55% ee) a nitro-aldol reaction, compared to corresponding monomeric catalyst. A bimetallic mechanism is suggested by kinetic experiment showing that law second order [catalyst]. self-assembly hydrogen bonding was...

The design and solution-phase synthesis of an α-helix mimetic library as integral component a small-molecule targeting protein−protein interactions are described. iterative design, synthesis, evaluation the candidate was initiated from precedented triaryl template refined by screening designs for inhibition MDM2/p53 binding. Upon identifying chemically biologically satisfactory consistent with capabilities academic collaborators, corresponding complete assembled 400 mixtures 20 compounds (20...

A cooperative catalyst that features urea H-bonding and a cobalt center was developed for anti-selective asymmetric Henry reactions (see scheme). The H-bonds of play crucial role in the improvement yield (from 30 % to 84 %), enantioselectivity 78 96 anti diastereoselectivity 3:1 48:1). short synthesis (1R,2S)-methoxamine hydrochloride also accomplished with this catalyst. Detailed facts importance specialist readers are published as "Supporting Information". Such documents peer-reviewed, but...

Abstract Extreme ultraviolet (EUV) lithography has enabled significant reductions in device dimensions but is often limited by capillary force‐driven pattern collapse conventional wet processes. Recent dry‐development approaches, while promising, frequently require toxic etchants or specialized equipment, limiting their broader applicability and highlighting the need for more sustainable, cost‐effective alternatives. In this study, highly reactive, etchant‐free dry‐developable EUV...

Organolanthanide complexes of the general type Cp'(2)LnCH(TMS)(2) (Cp' = eta(5)-Me(5)C(5); Ln La, Sm, Y; TMS SiMe(3)) and CGCSmN(TMS)(2) (CGC Me(2)Si(eta(5)-Me(4)C(5))((t)()BuN)) serve as effective precatalysts for rapid, regioselective, highly diastereoselective intramolecular hydroamination/cyclization primary secondary amines tethered to conjugated dienes. The rates aminodiene cyclizations are significantly more rapid than those corresponding aminoalkenes. This dienyl group rate...

New chiral C1-symmetric organolanthanide catalysts of the type Me2Si(OHF)(CpR*)LnN(TMS)2 (OHF = η5-octahydrofluorenyl; Cp η5-C5H3; R* (−)-menthyl; Ln Sm, Y, Lu; TMS SiMe3) have been synthesized, characterized, and implemented in enantioselective diastereoselective cyclizations aminoalkenes phosphinoalkenes. Me2Si(OHF)(CpR*)LnCl2-Li(DME)2+ catalyst precursors can be prepared up to ∼90% diastereomeric purity then converted into corresponding amido catalysts, which isolated ∼100% after...

Efficient intramolecular hydroamination/cyclization of primary and secondary conjugated aminodienes can be effected by using organolanthanide precatalysts the type Cp'2LnCH(TMS)2 (Cp' = eta5-Me5C5; Ln La, Sm, Y; TMS SiMe3) CGCSmN(TMS)2 (CGC Me2Si(eta5-Me4C5)(tBuN)). The transformation proceeds cleanly (>/= 90% conversion) at 25-60 degrees C with good rates high regioselectivities, electronic effects leading to significant rate enhancements. Some features reaction parallel monosubstituted...

Among the agents classified as "Category A" by U.S. Centers for Disease Control and Prevention, botulinum neurotoxin (BoNT) is most toxic protein known, with microgram quantities of causing severe morbidity mortality oral or i.v. routes. Given that this toxin easily could be used in a potential bioterrorist attack, countermeasures urgently are needed to counteract pathophysiology BoNT. At molecular level, BoNT exerts its paralytic effects through intracellular cleavage vesicle docking...

C 1-symmetric isoquinoline-based chiral diaminocarbene ligands (MIQ) have been developed to block three quadrants of the metal coordination sphere, complementing C2-symmetric biisoquinoline-based (BIQ). MIQ-Cu complexes catalyzed conjugate borylation various α,β-unsaturated amides in good yields (82–99%) and enantioselectivities (75–87% ee).

Base-functionalized aza-bis(oxazoline) ligands were prepared to explore the concept of dual activation through Lewis acid and a tethered tertiary amine base. The catalytic activity Cu complex was evaluated for asymmetric Henry reaction. Compared with corresponding unfunctionalized copper external 1-benzyl-4-ethylpiperazine base, ethylpiperazine-functionalized catalyst resulted in rate acceleration (2.5 times) as well improved enantioselectivity (72% ee vs 92% ee).

Sterically demanding and conformationally stable N,N′-ditertiaryalkyl-N,N′-diphenyl acyclic diaminocarbenes (ADCs) were developed. Bulky ADC−Au catalysts not only showed competitive reactivities in hydroamination enyne cyclization but also demonstrated unique ligand properties different from bulky N-heterocyclic carbene (NHC) counterparts.

Polypyrrole multilayer-laminated cellulose was fabricated<italic>via</italic>vapor-phase polymerization and employed as a cost-effective adsorbent hybrid material removing potentially toxic metal ions with high adsorption efficiency good recyclability even on large scale (&gt;1 liter).

Recently, perovskite solar cells (PSCs) have emerged as an excellent photovoltaic device owing to the outstanding power conversion efficiency (PCE). Nevertheless, instability remains a critical issue in this field. To overcome without deteriorating PCE, dopant-free hole transporting materials (HTMs) are needed separate air-sensitive layer from extrinsic factors, which induce its degradation. Herein, we developed novel conjugate polymers of benzo[1,2-b:4,5-b′]dithiophene (BDT) and...

Mixed-phase palladium selenides (PdxSey) were synthesized using a single organometallic precursor, offering precise control over the phase distribution and enabling comprehensive study of phase-dependent electrocatalytic performance. Rietveld refinement X-ray diffraction data supported by inductively coupled plasma mass spectrometry photoelectron spectroscopy analyses revealed progressive transition from Se-rich (PdSe2) to Se-deficient (Pd34Se11) phases with increasing synthesis temperature....

A new class of biaryl Imidazo[1,5‐a]pyridin‐3‐ylidene (ImPy) ligands featuring a Cu‐F interaction and C5‐aryl substituent were developed for the diastereoselective addition reactions easily accessible olefins to ketones. X‐ray noncovalent (NCI) analysis indeed demonstrated presence Cu‐arene in F‐ImPy‐Cu catalyst. The complex is an effective catalyst 1,3‐enyne nucleophile ketones, showing up 96% yields &gt;10:1 diastereoselectivities.

Chiral biisoquinoline-based diaminocarbene ligands (BIQ) were designed to create a chiral environment extended toward the metal center, which was confirmed by an X-ray structure. The concise ligand synthesis is highlighted modified Bischler-Napieralski cyclization of bisamides prepared from readily available phenethylamines, and allows easy variation stereodifferentiating groups. cyclohexyl-BIQ-copper complex efficient catalyst for enantioselective SN2' allylic alkylation with Grignard...

N-heterocyclic carbenes (NHCs) serve as highly proficient ligands in many transition metal catalyzed reactions. As such, significant efforts have been devoted to the extension of NHCs into field asymmetric catalysis. Development was slow at first but is now rapidly accelerating, evidenced by increase number transformations displaying excellent enantioselectivities. Chronicled here are attempts catalysis with NHC ligands, and results categorized effecting well type reaction. Ruthenium,...

We demonstrate that small-molecule organic thin films of pentacene deposited from thermal and supersonic molecular beam sources can undergo significant reorganization under vacuum or in N2 atmosphere, beginning immediately after deposition onto SiO2 gate dielectric treated with hexamethyldisilazane (HMDS) fluorinated octyltrichlorosilane (FOTS). Films on bare remain unchanged even extended aging vacuum. The changes observed low-energy surfaces include the depletion molecules interfacial...

Abstract A series of novel bis‐urea‐functionalized (salen)Co complexes has been developed. The were designed to form self‐assembled structures in solution through intermolecular urea–urea hydrogen‐bonding interactions. These bis‐urea catalysts resulted rate acceleration (up 13 times) the hydrolytic kinetic resolution (HKR) rac ‐epichlorohydrin THF by facilitating cooperative activation, compared monomeric catalyst. In addition, one III catalyst efficiently resolves various terminal epoxides...

The first palladium-catalyzed enantioselective conjugate addition reactions of arylboronic acids to 2-substituted chromones with chiral pyridine-dihydroisoquinoline ligands have been developed.