Abstract Tin‐based halide perovskite materials have been successfully employed in lead‐free solar cells, but the overall power conversion efficiencies (PCEs) limited by high carrier concentration from facile oxidation of Sn 2+ to 4+ . Now a chemical route is developed for fabrication high‐quality methylammonium tin iodide (MASnI 3 ) films: hydrazinium (HASnI film first solution‐deposited using presursors (HAI) and (SnI 2 ), then transformed into MASnI via cation displacement approach. With...

Carboranyl amines are distinct from typical organic amines. Due to the electronic influence of carborane cage, they have low nucleophilicity and reluctant alkylate. Moreover, asymmetric synthesis chiral carboranes is still in its infancy. Herein we achieved first catalytic N-alkylation o-carboranyl amine, providing general access diverse secondary with high efficiency enantioselectivity under mild conditions. For time, organocatalysis was introduced chemistry. Key success use situ generated...

Abstract Presented herein is an intriguing effect of fluorine, and it allows difluoroenol silyl ethers to couple with aryliodanes in a redox‐neutral manner afford ortho ‐iodo difluoroalkylated arenes. The remaining iodide group provides versatile platform for converting the products into various valuable reaction shows excellent functional‐group compatibility broad substrate scope. A DFT mechanistic study suggests that fluorine facilitates subtle nucleophilic attack oxygen atom enol onto...

The sigma (σ)-hole effect has emerged as a promising tool to construct novel architectures endowed with new properties. A simple yet effective strategy for the generation of monofluoromethyl radicals is continuing challenge within synthetic community. Fluoromethylphosphonium salts are easily available, air- and thermally stable, well simple-to-handle. Herein, we report ability σ-hole facilitate visible-light-triggered photolysis phosphonium iodide salts, charge-transfer complex, selectively...

Enantioselective synthesis of isoxazolines bearing allenes by palladium catalyzed carboetherification alkenyl oximes with propargylic acetates. DFT calculations carried out to disclose the detailed mechanism and origins enantioselectivity.

Catalytic enantioselective α-chlorination of ketones is a highly desirable process. Different from the conventional approaches that employ corrosive electrophilic chlorination reagents, process disclosed here employs nucleophilic chloride, aqueous NaCl solution, and even seawater, as green inexpensive chlorine sources. This mechanistically distinct electronically opposite approach provides facile access to diverse enantioenriched acyclic α-chloro are less straightforward by approaches. With...

A highly efficient palladium-catalyzed asymmetric tandem aza-Heck/Sonogashira coupling reaction of O-phenyl hydroxamic ethers with terminal alkynes is described. This protocol enables versatile access to challenging chiral isoindolinone derivatives bearing a quaternary stereogenic center. The aminoalkynylation shows broad functional group tolerance and allows the straightforward preparation isoindolinones high efficiency excellent enantioselectivity under mild conditions. DFT calculations...

We herein report a robust catalyst-free cross-coupling between ArI(OAc)2 and α-stannyl nitriles, aided by TMSOTf. The transformation introduces cyanoalkyl group to the ortho position of simultaneously reduces aryl iodine(III) iodide, thus providing α-(2-iodoaryl) nitrile as product. This could be completed within 5 min at -78 °C features superb functional-group tolerance efficient scalability. DFT calculations indicate that formation ketenimine(aryl)iodonium intermediate subsequent...

β,γ-Unsaturated esters are building blocks in biologically important compounds, pharmaceuticals, and natural products. Because the current synthetic methods often require transition-metal catalysts or lack general variants, we herein describe a simple NaI-involved photoinduced deaminative alkenylation for their synthesis absence of photocatalysts additives. The density functional theory study unveils that electrostatic interaction NaI with Katritzky salts is key to forming photoactive...

The T center in silicon has recently emerged as a promising candidate for scalable quantum technologies, due to its telecommunications band optical transition and microwave addressable ground state spin. immense promise of the is driven by host material; far most mature, manufacturable semiconductor material integrated photonic electronic devices. Here, we present first study T-centers an electrical device. We ensemble centers coupled buried lateral P-I-N diode silicon, observing T-center's...

Disclosed here is a catalytic enantioselective nucleophilic α-fluorination of simple ketones. A new hydrogen bonding donor catalyst was designed to not only overcome the competing deactivation but also enable efficient enantiocontrol in C–F bond formation between racemic α-keto sulfoniums and CsF. Careful condition optimization resulted general mild protocol applicable for configurational flexible acyclic α-fluoro ketones bearing tertiary stereogenic center, thus complementary previous...

Iridium‐catalyzed asymmetric allenylic substitution represents a useful method for the construction of allenes bearing an central chirality, but current success has uniformly relied on only one specific chiral bidentate ligand. Herein we address limitation by design new type monodentate ligands leading to not excellent enantiocontrol in substitution, also efficient kinetic resolution α‐allenylic alcohols, phenomenon never observed before iridium‐catalyzed substitution. This is rare...

Iridium‐catalyzed asymmetric allenylic substitution represents a useful method for the construction of allenes bearing an central chirality, but current success has uniformly relied on only one specific chiral bidentate ligand. Herein we address limitation by design new type monodentate ligands leading to not excellent enantiocontrol in substitution, also efficient kinetic resolution α‐allenylic alcohols, phenomenon never observed before iridium‐catalyzed substitution. This is rare...

A DFT comparative mechanistic study unveils that the TBD-catalyzed reactions of amines with CO2 and hydrosilanes may either undergo a neutral mechanism or involving free ions, depending on polarity solvent. The nucleophilicity is an important factor to determine chemoselectivities give formamide aminal/N-methylated amine.

Density functional theory mechanistic study has been carried out to account for the base-free nickel-catalyzed Suzuki-Miyaura coupling of acid fluorides (ArC(O)F) with boronic acids (Ar'B(OH)2). After oxidative addition break C-F bond fluoride, resultant ArC(O)[Ni]F species undergoes transmetalation Ar'B(OH)2 give ArC(O)[Ni]Ar'. Subsequently, ArC(O)[Ni]Ar' can either undergo decarbonylation, finally leading product (ArAr'), or reductive elimination ketone byproduct ArC(O)Ar'. The kinetic...

Abstract Methylammonium iodide (MAI) and lead (PbI 2 ) have been extensively employed as precursors for solution‐processed MAPbI 3 perovskite solar cells (PSCs). However, the films directly deposited from precursor solutions, usually suffer poor surface coverage due to uncontrolled nucleation crystal growth of during film formation, resulting in low photovoltaic conversion efficiency reproducibility. Herein, propylammonium PbI are solution deposition (PAPbI film. It is found that good...

Abstract We herein report a robust catalyst‐free cross‐coupling between ArI(OAc) 2 and α‐stannyl nitriles, aided by TMSOTf. The transformation introduces cyanoalkyl group to the ortho position of simultaneously reduces aryl iodine(III) iodide, thus providing α‐(2‐iodoaryl) nitrile as product. This could be completed within 5 min at −78 °C features superb functional‐group tolerance efficient scalability. DFT calculations indicate that formation ketenimine(aryl)iodonium intermediate subsequent...

A straightforward photoinduced NHN-catalyzed method for generating nucleophilic selenolates from diselenides without the need of stoichiometric reductants.

Catalytic enantioselective substitution of the readily available racemic α-halo carbonyl compounds by nitrogen nucleophiles represents one most convenient and direct approaches to access enantioenriched α-amino compounds. Distinct from two strategies involving radicals enolate ions, herein we have developed a new protocol featuring an electronically opposite way weaken/cleave carbon–halogen bond. A suitable chiral anion-based catalyst enables effective asymmetric control over key positively...

The enantioconvergent alkyl–alkyl coupling involves two competitive catalytic cycles with nickel(0) and nickel( i ) active catalysts, respectively. K 3 PO 4 plays a crucial role to enable the hydride transfer from hydrosilane nickel–bromine species.

We report an efficient and versatile catalytic N-heterocyclic nitrenium charge transfer complex strategy for the single-electron reduction of chloroform, resulting in generation dichloromethyl radical use various transformations.

Abstract Presented herein is an intriguing effect of fluorine, and it allows difluoroenol silyl ethers to couple with aryliodanes in a redox‐neutral manner afford ortho ‐iodo difluoroalkylated arenes. The remaining iodide group provides versatile platform for converting the products into various valuable reaction shows excellent functional‐group compatibility broad substrate scope. A DFT mechanistic study suggests that fluorine facilitates subtle nucleophilic attack oxygen atom enol onto...

Abstract Tin‐based halide perovskite materials have been successfully employed in lead‐free solar cells, but the overall power conversion efficiencies (PCEs) limited by high carrier concentration from facile oxidation of Sn 2+ to 4+ . Now a chemical route is developed for fabrication high‐quality methylammonium tin iodide (MASnI 3 ) films: hydrazinium (HASnI film first solution‐deposited using presursors (HAI) and (SnI 2 ), then transformed into MASnI via cation displacement approach. With...

Open AccessCCS ChemistryRESEARCH ARTICLE1 Oct 2019Intramolecular α-Oxygenation of Amines via N-Heterocyclic Carbene-Catalyzed Domino Reaction Aryl Aldehyde: Experiment and DFT Calculation Xiang-Yu Chen, Chao-Shen Zhang, Liang Yi, Zhong-Hua Gao, Zhi-Xiang Wang Song Ye Chen Beijing National Laboratory for Molecular Sciences, CAS Key Recognition Function, Research/Education Center Excellence in Institute Chemistry, Chinese Academy 100190 (China) , Zhang School Chemical University the 100049 Yi...

The Boekelheide rearrangement is often employed for the oxy-functionalization of alkyl groups in 2-position pyridines, yet corresponding alkylation reaction has so far not been realized since 1954. N-Alkenoxypyridinium functionalization widely applied to synthesize various carbonyl compounds by only using unit. Herein, we describe a simple efficient N-alkenoxypyridiniums through synthesis β-2-pyridyl ketones.