A static precise single-point positioning method based on carrier phase zero-baseline self-differencing.

Satellite navigation positioning has become an indispensable component of everyday life, where precise pinpointing and rapid convergence are crucial in delivering timely and accurate location information. However, due to the damping of integer ambiguities and system residual errors, the rapid convergence of Precise Point Positioning (PPP) implementation is a significant challenge. To address this, this paper proposes a novel Carrier Phase Zero-Baseline Self-Differencing Precise Point Positioning (CZS-PPP) technique and its ionosphere-free fusion model. By employing the proposed CZS-PPP approach in separate scenarios involving BDS-3, GPS, and dual-system settings, we systematically validate the efficacy of the method. The experimental results indicate that the convergence time of the method is less than 4 min in a single-system scenario. Furthermore, in a dual-system scenario, the method can achieve rapid convergence in less than 3 min. The CZS-PPP technique presented demonstrates the elimination of integer ambiguities and the effective suppression of system residuals, in comparison to the conventional method. The proposed approach has demonstrated remarkable performance across different systems, offering a promising new pathway for achieving PPP fast convergence in BDS/GNSS.

Late-Stage Diversification of Phosphines by C-H Activation: A Robust Strategy for Ligand Design and Preparation.

ConspectusThe advent of the twenty-first century marked a golden era in the realm of synthetic chemistry, exemplified by groundbreaking advancements in the field of C-H activation, which is a concept that quickly transitioned from mere academic fascination to an essential element within the synthetic chemist's toolkit. This methodological breakthrough has given rise to a wealth of opportunities spanning a wide range of chemical disciplines. It has facilitated the late-stage diversification of elaborate organic frameworks, encompassing the spectrum from simple methane to complex polymers, thus refining the lead optimization process and easing the production of diverse molecular analogues. Among these strides forward, the development of phosphorus(III)-directed C-H activation stands out as an increasingly significant and inventive approach for the design and synthesis of ligands, substantially redefining the contours of synthetic methodology.Phosphines, renowned for their roles as ligands and organocatalysts, have become fundamentally important in modern organic chemistry. Their efficiency as ligands is significantly affected by coordination with transition metals, which is essential for their involvement in catalytic processes, influencing both the catalytic activity and the selectivity. Historically, the fabrication of phosphines predominantly relied on synthesis employing complex, multistep procedures. Addressing this limitation, our research has delved into ligand design and synthesis through innovative catalytic P(III)-directed C-H activation strategies. In this Account, we have explored a spectrum of procedures, including direct arylation using metal catalysis, and ventured further into domains such as C-H alkylation, alkenylation, aminocarbonylation, alkynylation, borylation, and silylation. These advances have enriched the field by providing efficient methods for the late-stage diversification of biaryl-type monophosphines as well as enabled the C-H activation of triphenylphosphine and its derivatives. Moreover, we have successfully constructed libraries of diverse axially chiral binaphthyl phosphine ligands, showcasing their potency in asymmetric catalysis. Through this Account, we aim to illuminate the exciting possibilities presented by P(III)-directed C-H activation in propelling the boundaries of organic synthesis. By highlighting our pioneering work, we hope to inspire further developments in this promising field of chemistry.

Enantioselective Rhodium-Catalyzed C-H Arylation Enables Direct Synthesis of Atropisomeric Phosphines.

Atropisomeric phosphines hold considerable significance in asymmetric catalysis, yet their synthesis presents a formidable challenge owing to intricate multistep procedures. In this context, a groundbreaking methodology has been presented for their preparation. This innovative approach entails an atroposelective rhodium-catalyzed C-H activation employing aryl and heteroaryl halides, chelated by a P(III) center. The essence of this strategy lies in its ability to directly construct chiral phosphine ligands in a single step, thereby exhibiting exceptional efficiency in terms of atom and redox economy. Illustrative examples serve to demonstrate the immense potential of in situ-formed ligands in asymmetric catalysis. Mechanistic experiments have further provided invaluable insights into this transformation.

Atroposelective hydroarylation of biaryl phosphines directed by phosphorus centres.

Prized for their ability to generate chemical complexity rapidly, catalytic carbon-hydrogen (C-H) activation and functionalization reactions have enabled a paradigm shift in the standard logic of synthetic chemistry. Directing group strategies have been used extensively in C-H activation reactions to control regio- and enantioselectivity with transition metal catalysts. However, current methods rely heavily on coordination with nitrogen and/or oxygen atoms in molecules and have therefore been found to exhibit limited generality in asymmetric syntheses. Here, we report enantioselective C-H activation with unsaturated hydrocarbons directed by phosphorus centres to rapidly construct libraries of axially chiral phosphines through dynamic kinetic resolution. High reactivity and enantioselectivity are derived from modular assembly of an iridium catalyst with an endogenous phosphorus atom and an exogenous chiral phosphorus ligand, as confirmed by detailed experimental and computational studies. This reaction mode significantly expands the pool of enantiomerically enriched functional phosphines, some of which have shown excellent efficiency for asymmetric catalysis.

Multi-scale hybrid spherical graphite composites: a light weight thermal interface material with high thermal conductivity and simple processing technology.

In consideration of low density and high intrinsic thermal conductivity, spherical graphite powders can act as promising fillers for light weight thermal interface materials. Herein, spherical artificial graphite derived composites exhibit a similar thermal conductivity and significantly reduced bulk density compared with traditional Al2O3-derived composites. Further, based on the particle packing theory, an innovatively optimized calculation method has been proposed by introducing the quadratic programming method into the traditional calculation method to acquire the optimum formulation of multi-scale spherical graphite particles. The thermal conductivity of the optimum formulation-derived composites attains 1.994 W m-1 K-1, which is 1.72 times higher than that of the single particle size-derived composites (1.156 W m-1 K-1), accompanied by a low density of 1.812 g cm-3 vs. the 2.31 g cm-3 of the traditional Al2O3-derived composites. Besides, the relationships between the tap density of the graphite powders, thermal conductivity and maximum filling content of the composites are creatively established, which are available for predicting the thermal conductivities of composites by simply testing the tap density of the fillers. This present work provides an instructional strategy to optimize spherical filler particles for thermal management of electronic devices.

Radical Addition Enables 1,2-Aryl Migration from a Vinyl-Substituted All-Carbon Quaternary Center.

An efficient method for photocatalytic perfluoroalkylation of vinyl-substituted all-carbon quaternary centers involving 1,2-aryl migration has been developed. The rearrangement reactions use fac-Ir(ppy)3 , visible light and commercially available fluoroalkyl halides and can generate valuable multisubstituted perfluoroalkylated compounds in a single step that would be challenging to prepare by other methods. Mechanistically, the photoinduced alkyl radical addition to an alkene leads to the migration of a vicinal aryl substituent from its adjacent all-carbon quaternary center with the concomitant generation of a C-radical bearing two electron-withdrawing groups that is further reduced by a hydrogen donor to complete the domino sequence.

An Olefinic 1,2-Boryl-Migration Enabled by Radical Addition: Construction of gem-Bis(boryl)alkanes.

A series of in situ formed alkenyl diboronate complexes from alkenyl Grignard reagents (commercially available or prepared from alkenyl bromides and Mg) with B2 Pin2 (bis(pinacolato)diboron) react with diverse alkyl halides by a Ru photocatalyst to give various gem-bis(boryl)alkanes. Alkyl radicals add efficiently to the alkenyl diboronate complexes, and the adduct radical anions undergo radical-polar crossover, specifically, a 1,2-boryl-anion shift from boron to the α-carbon sp2 center. This transformation shows good functional-group compatibility and can serve as a powerful synthetic tool for late-stage functionalization in complex compounds. Measurements of the quantum yield reveal that a radical-chain mechanism is operative in which the alkenyl diboronates acts as reductive quencher for the excited state of the photocatalyst.

Enantioselective Copper-Catalyzed Defluoroalkylation Using Arylboronate-Activated Alkyl Grignard Reagents.

A copper-catalyzed system has been introduced for the enantioselective defluoroalkylation of linear 1-(trifluoromethyl)alkenes through C-F activation to synthesize various gem-difluoroalkenes as carbonyl mimics. For the first time, arylboronate-activated alkyl Grignard reagents were uncovered in this cross-coupling reaction. Mechanistic studies confirmed that the tetraorganoborate complexes generated in situ were the key reactive species for this transformation.

Ru/Cu Photoredox or Cu/Ag Catalyzed C4-H Sulfonylation of 1-Naphthylamides at Room Temperature.

A mild and efficient protocol for C4-H sulfonylation of 1-naphthylamine derivatives with sodium sulfinates has been described. This C4 sulfonylation proceeded smoothly at room temperature under Ru/Cu photoredox catalysis or Cu/Ag cocatalysis and could tolerate various functional groups. In addition, control experiments suggested that this C4-H sulfonylation reaction might proceed via a single-electron-transfer process.

Palladium-Catalyzed Regioselective C8-H Amination of 1-Naphthylamine Derivatives with Aliphatic Amines.

A simple and facile protocol for palladium-catalyzed picolinamide-directed C8-H amination of 1-naphthylamine derivatives with simple secondary aliphatic amines was developed, thereby providing a new route to 1,8-naphthalenediamine derivatives. It is noteworthy that the picolinamide moiety as a bidentate directing group may play a key role in this regioselective transformation.